Fruit peel waste as a novel low-cost bio adsorbent - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Reviews in Chemical Engineering, 2015)
Fruit peel waste (FPW) is abundantly available from the agricultural and food processing industry and has been studied in recent past as an adsorbent. This paper critically reviews the reported work and investigates various FPW-pollutant systems. The study includes statistics of FPW generation, modification, characterization, adsorption ability, recovery/regeneration, and modeling (isotherms, kinetics, and thermodynamics) of batch adsorption. It is found that orange and banana peels are the most extensively studied adsorbents, whereas Pb2+ and methylene blue are the most efficiently removed pollutants, the Langmuir and Freundlich adsorption isotherms provide the best fit in most of the cases, and in general, pseudo-second-order kinetics is followed. There are very limited column studies and no report on commercial plant. Though the reproducibility of the results is poor, FPW has a great potential in the wastewater treatment due to its abundant and cheap availability. FPW can be used for removal of heavy metals and dyes; however, removal of organic and gaseous impurities needs further investigation.
Keywords: adsorbent; Adsorption; fruit peel waste; organic and inorganic pollutants; wastewater

Functional characterization of novel sesquiterpene synthases from Indian sandalwood, santalum album - Srivastava, Prabhakar Lal; Daramwar, Pankaj P.; Krithika, Ramakrishnan; Pandreka, Avinash; Shankar, S. Shiva; Thulasiram, Hirekodathakallu V. (Scientific Reports, 2015)
Indian Sandalwood, Santalum album L. is highly valued for its fragrant heartwood oil and is dominated by a blend of sesquiterpenes. Sesquiterpenes are formed through cyclization of farnesyl diphosphate (FPP), catalyzed by metal dependent terpene cyclases. This report describes the cloning and functional characterization of five genes, which encode two sesquisabinene synthases (SaSQS1, SaSQS2), bisabolene synthase (SaBS), santalene synthase (SaSS) and farnesyl diphosphate synthase (SaFDS) using the transcriptome sequencing of S. album. Using Illumina next generation sequencing, 33.32 million high quality raw reads were generated, which were assembled into 84,094 unigenes with an average length of 494.17 bp. Based on the transcriptome sequencing, five sesquiterpene synthases SaFDS, SaSQS1, SaSQS2, SaBS and SaSS involved in the biosynthesis of FPP, sesquisabinene, beta-bisabolene and santalenes, respectively, were cloned and functionally characterized. Novel sesquiterpene synthases (SaSQS1 and SaSQS2) were characterized as isoforms of sesquisabinene synthase with varying kinetic parameters and expression levels. Furthermore, the feasibility of microbial production of sesquisabinene from both the unigenes, SaSQS1 and SaSQS2 in non-optimized bacterial cell for the preparative scale production of sesquisabinene has been demonstrated. These results may pave the way for in vivo production of sandalwood sesquiterpenes in genetically tractable heterologous systems.

Gedunin and azadiradione: human pancreatic alpha-amylase inhibiting limonoids from neem (azadirachta indica) as anti-diabetic agents - Ponnusamy, Sudha; Haldar, Saikat; Mulani, Fayaj A.; Smita S. Zinjarde; Thulasiram, Hirekodathakallu; RaviKumar, Ameeta (Plos One, 2015)
Human pancreatic alpha-amylase (HPA) inhibitors offer an effective strategy to lower postprandial hyperglycemia via control of starch breakdown. Limonoids from Azadirachta indica known for their therapeutic potential were screened for pancreatic alpha-amylase inhibition, a known anti-diabetic target. Studies were carried out to reveal their mode of action so as to justify their hypoglycemic potential. Of the nine limonoids isolated/semi-synthesized from A. indica and screened for alpha-amylase inhibition, azadiradione and exhibited potential inhibition with an IC50 value of 74.17 and 68.38 mu M, respectively against HPA under in vitro conditions. Further screening on AR42J alpha-amylase secretory cell line for cytotoxicity and bioactivity revealed that azadiradione and gedunin exhibited cytotoxicity with IC50 of 11.1 and 13.4 mu M. Maximal secreted alpha-amylase inhibition of 41.8% and 53.4% was seen at 3.5 and 3.3 mu M, respectively. Michaelis-Menten kinetics suggested a mixed mode of inhibition with maltopentaose (K-i 42.2, 18.6 mu M) and starch (K-i' 75.8, 37.4 mu M) as substrate with a stiochiometry of 1: 1 for both azadiradione and gedunin, respectively. The molecular docking simulation indicated plausible p-alkyl and alkyl-alkyl interactions between the aromatic amino acids and inhibitors. Fluorescence and CD confirmed the involvement of tryptophan and tyrosine in ligand binding to HPA. Thermodynamic parameters suggested that binding is enthalpically and entropically driven with Delta G degrees of -21.25 kJ mol(-1) and -21.16 kJ mol(-1) for azadiradione and gedunin, respectively. Thus, the limonoids azadiradione and gedunin could bind and inactivate HPA (anti-diabetic target) and may prove to be lead drug candidates to reduce/control post-prandial hyperglycemia.

Gelation landscape engineering using a multi-reaction supramolecular hydrogelator system - Foster, Jamie S.; Zurek, Justyna M.; Almeida, Nuno M. S.; Hendriksen, Wouter E.; le Sage, Vincent A. A.; Lakshminarayanan, Vasudevan; Thompson, Amber L.; Banerjee, Rahul; Eelkema, Rienk; Mulvana, Helen; Paterson, Martin J.; van Esch, Jan H.; et al. (Journal of the American Chemical Society, 2015)
Simultaneous control of the kinetics and thermodynamics of two different types of covalent chemistry allows pathway selectivity in the formation of hydrogelating molecules from a complex reaction network. This can lead to a range of hydrogel materials with vastly different properties, starting from a set of simple starting compounds and reaction conditions. Chemical reaction between a trialdehyde and the tuberculosis drug isoniazid can form one, two, or three hydrazone connectivity products, meaning kinetic gelation pathways can be addressed. Simultaneously, thermodynamics control the formation of either a keto or an enol tautomer of the products, again resulting in vastly different materials. Overall, this shows that careful navigation of a reaction landscape using both kinetic and thermodynamic selectivity can be used to control material selection from a complex reaction network.

Generic framework for crystallization processes using the population balance model and its applicability - Shaikh, Latif J.; Bari, Atul H.; Ranade, Vivek V.; Pandit, Aniruddha B. (Industrial & Engineering Chemistry Research, 2015)
A generic modeling framework for batch cooling crystallization processes has been developed to understand the crystallization process from operational and modeling point of view. The generic framework for crystallization process modeling incorporates the characteristic dimensions of crystals and polymorphic transformation, as well as the hydrodynamic mixing effects in the crystallizer. This Polyhedral Polymorphic Multizonal Population Balance (PPMPBM) model considers bottom-up and top-down approaches for specific systems with specific targets. The PPMPBM framework allows switching between complex and simple models to study different crystallization systems with different scenarios and combination thereof. This framework uses gPROMS software (PSE, UK) and the Microsoft Excel front-end, along with the Polytope module in Matlab, to predict the crystal size and shape evolution as well as supersaturation profiles inside the crystallizer, which can be implemented for various crystallization systems.

Genotype x environment interactions and QTL clusters underlying dough rheology traits in triticum aestivum L. - Prashant, Ramya; Mani, Elangovan; Rai, Richa; Gupta, R. K.; Tiwari, Ratan; Dholakia, Bhushan B.; Oak, Manoj; Roeder, Marion; Kadoo, Narendra Y.; Gupta, Vidya (Journal of Cereal Science, 2015)
Genetic dissection of dough rheology traits (DRT) in hexaploid wheat was carried out using nine mixograph characters evaluated in two consecutive years in three agro-climatic zones in India in an RIL population (HI977 x HD2329). Pearson correlations determined in each year-location indicated 15 stable trait inter-relationships among them but inconsistent correlations with loaf volume (LV) were observed. Using AMMI analysis we derived patterns in G x E interactions (GEI) indicating 6-47% contribution for the DRT. Composite interval mapping using a linkage map of 202 SSR markers identified 144 DRT QTLs of which, 96 were detected in single- and the rest in two to five year-locations. Sixteen QTL clusters located on ten chromosomes were identified and only three of them on chromosomes 1B, 5B and 6D involved LV QTLs. For each trait, majority of the DRT QTLs detected in single as well as multiple environments showed location-specificity and suggested that owing to GEI, breeding for wheat dough quality might need careful selection of QTLs targeted for individual agro-climatic zones. The inconsistent correlations of DRT and LV and differential locations of their QTLs in this population corroborated that using dough rheological traits alone to predict LV might pose challenges during wheat improvement. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: AMMI analysis; Dough rheology; Mixograph; QTL

Gold(I)/chiral brønsted acid catalyzed enantioselective hydroamination-hydroarylation of alkynes: effect of remote hydroxyl group in the reactivity and enantioselectivity - Shinde, Valmik S.; Mane, Manoj V.; Vanka, Kumar; Mallick, Arijit; Patil, Nitin T. (Chemistry - A European Journal, 2015)

Graphene nanoribbons as prospective field emitter - Khare, Ruchita T.; Shinde, Dhanraj B.; Bansode, Sanjeewani; More, Mahendra A.; Majumder, Mainak; Pillai, Vijayamohanan K.; Late, Dattatray J. (Applied Physics Letters, 2015)
Field emission characteristics of graphene nanoribbons (GNRs) synthesized by unzipping of multiwall carbon nanotubes using a facile hydrothermal route have been investigated at a base pressure of 1 x 10(-8) mbar. The values of turn-on field, required to draw an emission current densities of 1 and 10 mu A/cm(2), are found to be 2.8 and 5.8 V/mu m, respectively, and a maximum emission current density of 500 mu A/cm(2) has been drawn at an applied field of 9.8 V/mu m. The emission current stability of the GNRs emitter was studied at preset values of 1 and 10 mu A over a period of 3 h, and is found to be excellent. The field emission results demonstrated herein suggest that GNRs based field emitters can open up many opportunities for their potential utilization as large area field emitters in various vacuum micro-nanoelectronic devices such as flexible field emission displays, portable X-ray, and microwave tubes. (C) 2015 AIP Publishing LLC.

Green synthesis of silver nanoribbons from waste X-ray films using alkaline protease - Shankar, Shiv; Prasad, R. G. S. V.; Selvakannan, P. R.; Jaiswal, Lily; Laxman, Ryali Seeta (Materials Express, 2015)
This work illustrates a facile approach to synthesize silver nanoribbons from waste X-ray films using alkaline protease from Beauveria sp. MTCC 5184 (BAP). The green synthesized nanoribbons have been characterized by UV-Vis spectroscopy, TEM, and FTIR. The UV-visible spectra gave maximum absorbance at 400 nm. TEM micrograph showed well-dispersed silver nanoribbons with an average length of 200-400 nm. FTIR result demonstrated the respective bands of the silver nanoribbons and proteins. XRD data revealed crystalline nature of silver nanoribbons dominated with (111) facets. In vitro antibacterial activity in terms of minimum inhibitory concentrations (MIC) and minimum bactericidal concentration (MBC) showed 8/16 mu g/mL (MIC/MBC) against Staphylococcus aureus ATCC 29213 and 4/8 mu g/mL (MIC/MBC) against Escherichia coli ATCC 25922. The green synthesized silver nanoribbons showed excellent biocompatibility up to 40 mu g/mL concentrations on mouse fibroblast cell line (L929).
Keywords: Alkaline Protease; Characterization; Cytotoxicity; Silver Nanoribbons; Waste X-ray Film

Hierarchical CdS nanostructure by Lawesson's reagent and its enhanced photocatalytic hydrogen production - Pandit, Vikram U.; Arbuj, Sudhir S.; Hawaldar, Ranjit R.; Kshirsagar, Pradnya V.; Deshmukh, Amarsinh J.; Ambekar, Jalindar D.; Mulik, Uttam P.; Gosavi, Suresh W.; Kale, Bharat B. (RSC Advances, 2015)
Lawesson's reagent (LR) has been effectively exploited for the synthesis of hierarchical architectures of cadmium sulphide (CdS) nanostructures for the first time. The X-ray diffractograms of the as synthesised CdS nanostructures confirm the formation of hexagonal CdS. The broadness of the XRD peaks clearly indicates the nanocrystalline nature of CdS with average crystallite size of 4 nm. A FESEM study revealed the formation of hierarchical nanostructures, whereas a TEM study showed that the hierarchical arrangement is composed of nanosized CdS particles. A band-gap i.e. 2.4 eV was derived from diffuse reflectance spectroscopy. The photoluminescence spectrum showed an emission peak at 535 and 568 nm which can be attributed to band-edge emission and surface emissions or possible metal vacancies, respectively. Considering the band-gap within the visible region, the photocatalytic hydrogen evolution performance of these CdS nanostructures was performed under visible light irradiation from hydrogen sulphide and water, respectively. Utmost hydrogen evolution i.e. 14 136 mu mol h(-1) g(-1) and 2065 mu mol h(-1) g(-1) was observed over a naked CdS nanostructure via H2S and water decomposition, respectively. The amount of hydrogen obtained by H2S splitting is much higher as compared to earlier reports.

High performance single crystalline PbWO4 nanorod field effect transistor - Walke, Pravin S.; Patil, Vandana B.; Mulla, Imtiaz S.; Late, Dattatray J. (Journal of Materials Science-Materials in Electronics, 2015)
The highly crystalline PbWO4 nanorods were synthesized using simple co-precipitation method which has application in field effect transistor. The synthesized PbWO4 nanorods were characterized by XRD, Raman spectroscopy, TEM and HRTEM indicating highly crystalline nature. Field effect transistor was fabricated on pre-patterned 300 nm SiO2/Si substrates using photolithography technique with channel length 1 A mu m and width 20 A mu m. Thin film (similar to 100 nm) was made up of PbWO4 nanorods by spin coating on the pre-patterned device used as channel layer. The field effect mobility was observed to be 4.7 cm(2) V-1 s(-1) and I-ON/OFF ratio similar to 10(3) which is far better than the organic molecules due to single crystalline nature and rod like morphology of the PbWO4 providing direct path for charges to transport towards channel.

High surface area porous carbon for ultracapacitor application by pyrolysis of polystyrene containing pendant carboxylic acid groups prepared via click chemistry - Chhatre, Shraddha; Aravindan, Vanchiappan; Puthusseri, Dhanya; Banerjee, Abhik; Madhavi, Srinivasan; Wadgaonkar, Prakash P.; Ogale, Satishchandra B. (Materials Today Communications, 2015)

Highly emissive organic solids with remarkably broad color tunability based on N,C-chelate, four-coordinate organoborons - Shaikh, Aslam C.; Ranade, Dnyanesh S.; Thorat, Shridhar; Maity, Arunava; Kulkarni, Prasad P.; Gonnade, Rajesh G.; Munshi, Parthapratim; Patil, Nitin T. (Chemical Communications, 2015)
Molecular fluorophores based on N,C-chelate, four-coordinate organo-borons exhibit tunable solid-state emission colors that cover the whole visible region from blue to red. The emission color can be tuned through the substituents on either quinolines or the boron center.

Highly loaded well dispersed stable Ni species in NiXMg2AlOY nanocomposites: application to hydrogen production from bioethanol - Fang, Wenhao; Paul, Sebastien; Capron, Mickael; Biradar, Ankush V.; Shubhangi B. Umbarkar; Dongare, Mohan K.; Dumeignil, Franck; Jalowiecki-Duhamel, Louise (Applied Catalysis B-Environmental, 2015)
Inexpensive NiXMg2AlOY nanocomposites with high Ni content (Ni wt% > 40%) are developed as efficient catalysts for the sustainable hydrogen production from a mixture of ethanol and water at low temperature. The NiXMg2AlOY nanocomposites are composed of small and uniform nanoparticles (4-6 nm) of NiO, Ni-Mg-(Al)-O and/or MgO. The strong interactions existing between Ni2+ cations and Mg2+ and/or Al3+ cations either in the Ni-Mg-(Al)-O solid solution and/or at the interface of nanoparticles of NiO and/or Ni-Mg-(Al)-O make the catalyst highly active and stable. The behavior of the solids is analyzed in the presence of low and high concentrations of ethanol while maintaining a H2O/EtOH molar ratio of 3. The NiXMg2AlOY catalysts are shown to be efficient toward H-2 production between 250 and 650 degrees C. In the presence of low concentration of ethanol, on the highly loaded Ni compound (Ni12Mg2AlOY), total conversion of ethanol is obtained at 250 degrees C without formation of CO and carbon, and at 300 degrees C a H-2 yield of 3 mol moletEtOH(-1) is obtained without the formation of CO, exhibiting a remarkable stability with the time on stream even if some carbon is formed. In high concentration of ethanol, total conversion of ethanol is obtained at 450 degrees C on the highly loaded Ni compound (Ni12Mg2AlOY). In such conditions, a stable co-generation of carbon nanofibrous materials which amount increases with Ni content is also obtained. The catalytic stability is related to the type and morphology of the carbon species formed. The correlations among the catalyst properties, the catalytic performances and the characterizations are thoroughly discussed. (C) 2014 Elsevier B.V. All rights reserved.
Keywords: Ethanol; Hydrogen; Nanofibrous carbon; nickel oxide; Steam reforming

Highly regioselective isomerizing hydroformylation of long-chain internal olefins catalyzed by a rhodium bis(phosphite) complex - Pandey, Swechchha; Chikkali, Samir H. (ChemCatChem, 2015)
The single-step synthesis, coordination behavior, and application of a bis(phosphite) ligand in the isomerizing hydroformylation of internal olefins was investigated. Interestingly, high-pressure NMR spectroscopy investigations revealed unexpected inequivalency of the two phosphorus nuclei, which display bisequatorial coordination of the bis(phosphite) ligand in a trigonal bipyramidal rhodium complex. Upon employment in the isomerizing hydroformylation of the exceedingly challenging plant oil derived substrate methyl oleate, the bis(phosphite) rhodium complex revealed an unprecedented linear selectivity of 75%.
Keywords: alkenes; bis(phosphite)s; Hydroformylation; isomerization; Rhodium

High-throughput simulations of dimer and trimer assembly of membrane proteins. the DAFT approach - Wassenaar, Tsjerk A.; Pluhackova, Kristyna; Moussatova, Anastassiia; Sengupta, Durba; Marrink, Siewert-Jan; Tieleman, D. Peter; Boeckmann, Rainer A. (Journal of Chemical Theory and Computation, 2015)
Interactions between membrane proteins are of great biological significance and are consequently an important target for pharmacological intervention. Unfortunately, it is still difficult to obtain detailed views on such interactions, both experimentally, where the environment hampers atomic resolution investigation, and computationally, where the time and length scales are problematic. Coarse grain simulations have alleviated the later issue, but the slow movement through the bilayer, coupled to the long life times of nonoptimal dimers, still stands in the way of characterizing binding distributions. In this work, we present DAFT, a Docking Assay For Transmembrane components, developed to identify preferred binding orientations. The method builds on a program developed recently for generating custom membranes, called insane (INSert membrANE). The key feature of DAFT is the setup of starting structures, for which optimal periodic boundary conditions are devised. The purpose of DAFT is to perform a large number of simulations with different components, starting from unbiased noninteracting initial states, such that the simulations evolve collectively, in a manner reflecting the underlying energy landscape of interaction. The implementation and characteristic features of DAFT are explained, and the efficacy and relaxation properties of the method are explored for oligomerization of glycophorin A dimers, polyleucine dimers and trimers, MS1 trimers, and rhodopsin dimers. The results suggest that, for simple helices, such as GpA and polyleucine, in POPC/DOPC membranes series of 500 simulations of 500 ns each allow characterization of the helix dimer orientations and allow comparing associating and nonassociating components. However, the results also demonstrate that short simulations may suffer significantly from nonconvergence of the ensemble and that using too few simulations may obscure or distort features of the interaction distribution. For trimers, simulation times exceeding several microseconds appear needed, due to the increased complexity. Similarly, characterization of larger proteins, such as rhodopsin, takes longer time scales due to the slower diffusion and the increased complexity of binding interfaces. DAFT and its auxiliary programs have been made available from http://cgmartini.nl/, together with a working example.

Hollow tubular porous covalent organic framework (COF) nanostructures - Pachfule, Pradip; Kandmabeth, Sharath; Mallick, Arijit; Banerjee, Rahul (Chemical Communications, 2015)
Hollow and tubular TpPa-COF structures have been synthesized by template-assisted replication of nanometer sized ZnO-nanorods. The hollow structures composed of microporous TpPa shells have high periodicity, moderate porosity, chemical stability and capsule shaped morphology as revealed by X-ray diffraction, porosity measurements, and SEM and TEM analyses.

Human telomeric RNA G-quadruplex response to point mutation in the G-quartets - Agarwala, Prachi; Kumar, Santosh; Pandey, Satyaprakash; Maiti, Souvik (Journal of Physical Chemistry B, 2015)
Many putative G-quadruplex forming sequences have been predicted to exist in the human genome and transcriptome. As these sequences are subject to point mutations or SNPs (single nucleotide polymorphisms) during the course of evolution, we attempt to understand impact of these mutations in context of RNA G-quadruplex formation using human telomeric RNA (TERRA) as a model sequence. Our studies suggest that G-quadruplex stability is sensitive to substitution of the guanines comprising G-quartets. While central G-quartet plays a crucial role in maintaining the DNA G-quadruplex stability as evident in literature, there is equal importance of three G-quartets in the stability of RNA quadruplex structure. The work here highlights the alterations in the G-quartet are detrimental to the integrity of overall RNA G-quadruplex structure. Furthermore, TmPyP4 molecules are shown to exhibit similar binding behavior toward telomeric RNA G-quadruplex harboring base substitutions employing CD titrations and isothermal titration calorimetry; well indicating that mutation does not influence TmPyP4 recognition ability as it affects the stability of RNA G-quadruplex. Thus, our study implicates that mutation in G-quartets causes destabilization of RNA G-quadruplex without affecting its trans factor binding ability.

Hydrothermal synthesis and characterization of carbon nanospheres: a mechanistic insight - Bhagat, P. N.; Patil, K. R.; Bodas, Dhananjay S.; Paknikar, K. M. (RSC Advances, 2015)
Hydrothermally synthesized carbon nanospheres (CNS) follow a process of early nucleation followed by growth during synthesis. Here we report that growth occurs precisely after 5 min and prior to it nucleation occurs. The nucleation is a brief step in nanoparticle formation followed by growth of the nanoparticle depending on the reaction parameters.

Hyperhydrophilic three-dimensional crosslinked beads as an effective drug carrier in acidic medium: adsorption isotherm and kinetics appraisal - Mane, Sachin; Ponrathnam, Surendra; Chavan, Nayaku (New Journal of Chemistry, 2015)
Conventional drug delivery materials are known to provide slow and low drug loading in aqueous medium due to the hydrophobic or less hydrophilic properties of the carrier. However, the present study explored the synthesis of cheaply available metals modified with a hyperhydrophilic polymer. Hyperhydrophilic three-dimensional crosslinked beads as a drug carrier were synthesized with desirable properties that substantially influence the polymer efficiency. These synthesized polymers were characterized for surface area, particle size, acid content and morphology, and the metal modification was evaluated to obtain an efficient polymer for drug adsorption in an acidic medium. Contact time, which significantly affects drug adsorption was comparatively evaluated using the cheaply available metals, cobalt and nickel. Interestingly, an adsorption study revealed that gradual drug loading occurs during the initial 12 h. Afterwards, adsorption increases steadily and then stabilizes. Furthermore, theoretical predictions of adsorption, including Langmuir adsorption isotherm and pseudo order kinetics, were also evaluated. Remarkably, polymer supported Co/Ni demonstrated 85 and 78% metoprolol drug adsorption, respectively, at an optimum pH of 3 after 24 h. Langmuir adsorption isotherm revealed monolayer adsorption on the polymer supported Co/Ni. Pseudo first and second order kinetics were also evaluated and demonstrated the adsorption mechanism and equilibrium adsorption capacity, respectively.

Identifying solid luminogens through gold-catalysed intramolecular hydroarylation of alkynes - Shaikh, Aslam C.; Shalini, S.; Vaidhyanathan, Ramanathan; Mane, Manoj V.; Barui, Ayan Kumar; Patra, Chitta Ranjan; Venkatesh, Yeduru; Bangal, Prakriti Ranjan; Patil, Nitin T. (European Journal of Organic Chemistry, 2015)
The identification of a new class of luminogens based on pyrrolo-quinoxaline embedded coumarin (PQC) structures is reported. The reaction relies on the gold-catalyzed hydroarylation reaction of appropriately substituted aryl alkynoates that produces molecules that exhibit solvatochromism and aggregation-induced emission enhancement (AIEE) phenomena. The application of PQCs for live cell imaging has also been demonstrated.
Keywords: Cell imaging; Dyes/pigments; fluorescence; Gold; Luminescence; Solvatochromism

Impedimetric humidity sensor based on ?-Fe2O3 nanoparticles - Patil, U. V.; Rout, C. S.; Late, Dattatray J. (Advanced Device Materials, 2015)
Humidity sensing characteristics of thick-film sensors based on α-Fe2O3 nanoparticles synthesized by hydrothermal method have been reported. The as-synthesized α-Fe2O3 nanoparticles were characterized by using XRD, Raman spectroscopy, TEM and HRTEM. Our TEM result depicts that the size of α-Fe2O3 nanoparticles were in the range of 20–30 nm with highly crystalline nature. For humidity sensing experiment, the sensitivity of our α-Fe2O3 nanoparticles-based sensor device was found to be ∼99% and the fastest response times were noted, which indicate that the α-Fe2O3 nanoparticle-based humidity sensor device has more future prospects and demand. The humidity sensing properties of α-Fe2O3 nanoparticles seem to be associated to the sorption sites for the water molecules at the nanoparticles interfaces.

Implementation of the Z-vector method in the relativistic-coupled-cluster framework to calculate first-order energy derivatives: Application to the SrF molecule - Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2015)
The molecular dipole moment and magnetic hyperfine-structure constant demand an accurate wave function far from the nucleus and in the near nuclear region, respectively. We, therefore, employ the so-called Z-vector method in the domain of relativistic-coupled-cluster theory to calculate the first-order property of molecular systems in their open-shell ground-state configuration. The implemented method is applied to calculate the molecular dipole moment and parallel component of the magnetic hyperfine-structure constant of the SrF molecule. The results of our calculation are compared with the experimental and other available theoretically calculated values. We are successful in achieving good accordance with the experimental results. The result of our calculation of the molecular dipole moment is in the accuracy of similar to 0.5%, which is clearly an improvement over the previous calculation based on the expectation value method in the four-component coupled-cluster framework [V. S. Prasannaa et al., Phys. Rev. A 90, 052507 (2014)]. Thus, it can be inferred that the Z-vector method can provide an accurate wave function in both the near and far nuclear region, which is evident from our calculated results.

In silico ligand binding studies of cyanogenic beta-glucosidase, dhurrinase-2 from Sorghum bicolor - Mahajan, Chavi; Patel, Krunal; Khan, Bashir Mohammad; Rawal, Shuban S. (Journal of Molecular Modeling, 2015)
Dhurrinase, a cyanogenic beta-glucosidase from Sorghum bicolor is the key enzyme responsible for the hydrolysis of dhurrin to produce toxic hydrogen cyanide, as a part of plant defence mechanism. Dhurrinase 1 (SbDhr1) and dhurrinase 2 (SbDhr2), two isozymes have been isolated and characterized from S. bicolor. However, there is no information in the literature about the three dimensional (3D) structure of SbDhr2 and molecular interactions involved between the protein and ligand. In this study, the three dimensional structure of SbDhr2 was built based on homology modeling by using the X-ray crystallographic structure of its close homologue SbDhr1 as the template. The generated 3D model was energy minimized and the quality was validated by Ramachndran plot, various bioinformatic tools and their relevant parameters. Stability, folding-unfolding and flexibility of the modeled SbDhr2 was evaluated on the basis of RMSD, radius of gyration (R-g) and RMSF values respectively, obtained through molecular dynamic (MD) simulation. Further, molecular docking was performed with its natural substrate dhurrin, one substrate analogue, three un-natural substrates, and one inhibitor. Analysis of molecular interactions in the SbDhr2-ligand complexes revealed the key amino acid residues responsible to stabilize the ligands within the binding pocket through non-bonded interactions and some of them were found to be conserved (Glu239, Tyr381, Trp426, Glu454, Trp511). Reasonably broader substrate specificity of SbDhr2 was explained through the wider entrance passage observed in comparison to SbDhr1.
Keywords: beta-Glucosidase; Dhurrinase; Molecular docking; Molecular dynamic simulation; Sorghum bicolor

Influence of carbon and nitrogen source on growth, DON and NIV production by two species of fusarium isolated from finger millets - Penugonda, Shilpa; Rao, Vankudoth Koteswara; Rao, K. Narasimha; Sivadevuni, Girisham; Reddy, Solipuram Madhusudhan (International Journal of Pharmacy and Pharmaceutical Sciences, 2015)
Objective: Influence of different carbon [C] and nitrogen [N] source on the growth and Deoxynivalenol [DON] and Nivalenol [NIV] production by Fusarium aethiopicum and Fusarium culmorum was investigated. Methods: Seven days old monosporic cultures of F. aethiopicum strain GSKUMB [KJ21085] and F. culmorum strain GSKUMB [KJ190159] were grown in CYA broth and incubated at 27±2°C on the rotary shaker at 120 rpm for 21 days. At the end of incubation period, cultures were harvested for determination of fungal growth (biomass). The resultant culture filtrates were extracted twice with ethyl acetate and concentrated. One ml of final concentrate in methanol was employed for detection of DON and NIV with the help of RP-HPLC. Results: The highest amount of DON and NIV were produced by F. aethiopicum in the presence of D-mannose and D-galactose as C source, while the highest amount of biomass was recorded on maltose and succinic acid. F. culmorum produced maximum amount of toxins in the presence of D-glucose, D-mannitol and D-fructose. Sodium nitrate was most favorable nitrogen source as it induced maximum amount of toxins by F. aethiopicum, while L-methionine, L-asparatic acid and L-tryptophan were next preferred N source. In contrast, highest biomass of fungus was obtained with L-lysine, L-glutamine and L-tyrosine. F. culmorum produced maximum amount of toxin and biomass with potassium nitrate and L-tyrosine respectively. Conclusion: Present species of Fusarium differed varied both in toxins (DON, and NIV) and biomass production. Their response of fungi under investigation towards C and N sources is also varied.

Influence of different fusarium species on seed germination and seedlings growth of finger millet (Eleusine coracana L.) - Penugonda, Shilpa; Rao, Vankudoth Koteswara; Sivadevuni, Girisham; Reddy, Solipuram Madhusudhan (Indian Journal of Biotechnology, 2015)
Effect of agriculturally important Fusariumspecies on the seed germination and seedling growth of finger millet (Eleusine coracana L.) was investigated. Species of Fusarium caused significant seed germination inhibition and seedling growth which varied with the species and age of the culture. Culture filtrates of F. moniliforme, F. proliferatum, F. chlamydosporum, F. aethiopicum, F. heterosporum and F. sporotrichoides were comparatively more toxic. The correlation coefficients between polished and unpolished variety of fingermillet seed germination inhibition (0.574, P=0.005), shoot elongation inhibition (0.893, P=0.0000) and root elongation inhibition (0.175, P=0.1770) with culture filtrates of different species of Fusarium was recorded. Pathogenicity studies revealed that F. roseum, F.sporotrichoides, F. proliferatum and F.oxysporum caused seedrot and seedling death. The maximumroot elongation inhibition (52.20%), mean (36.39%) andminimum(14.73%)were recorded toward the toxicity of different species of Fusarium. Significant and positive correlation (0.802, P=0.0026) between the root and shoot, (0.393, P=0.130) between shoot and leaf, (0.121, P=0.369) between root and leaf elongation inhibition of finger millet could be observed. The culture filtrates ofmajormycotoxigenic strains of Fusariumrevealed production of Zearalenone (ZEA), T2 toxin, nivalenol (NIV), Deoxynivalenol (DON) and Deoxyscripenol (DAS). Toxicity of Fusarium species to its seed germination and seedling growth may be attributed to their secondary metabolites including mycotoxins.

Influence of macromolecular architecture on necking in polymer extrusion film casting process - Pol, Harshawardhan V.; Banik, Sourya; Azad, Lal Busher; Thete, Sumeet; Doshi, Pankaj; Lele, Ashish (30th International Conference of the Polymer-Processing-Society (PPS), 2015)
Extrusion film casting (EFC) is an important polymer processing technique that is used to produce several thousand tons of polymer films/coatings on an industrial scale. In this research, we are interested in understanding quantitatively how macromolecular chain architecture (for example long chain branching (LCB) or molecular weight distribution (MWD or PDI)) influences the necking and thickness distribution of extrusion cast films. We have used different polymer resins of linear and branched molecular architecture to produce extrusion cast films under controlled experimental conditions. The necking profiles of the films were imaged and the velocity profiles during EFC were monitored using particle tracking velocimetry (PTV) technique. Additionally, the temperature profiles were captured using an IR thermography and thickness profiles were calculated. The experimental results are compared with predictions of one-dimensional flow model of Silagy et al(1) wherein the polymer resin rheology is modeled using molecular constitutive equations such as the Rolie-Poly (RP) and extended Pom Pom (XPP). We demonstrate that the 1-D flow model containing the molecular constitutive equations provides new insights into the role of macromolecular chain architecture on film necking. D-1. Silagy, Y. Demay, and J-F. Agassant, Polym. Eng. Sci., 36, 2614 (1996).

Insights into the unfolding pathway and identification of thermally sensitive regions of phytase from aspergillus niger by molecular dynamics simulations - Kumar, Kapil; Patel, Krunal; Agrawal, Dinesh C.; Khire, Jayant Malhar (Journal of Molecular Modeling, 2015)
Thermal stability is of great importance in the application of commercial phytases. Phytase A (PhyA) is a monomeric protein comprising twelve alpha-helices and ten beta-sheets. Comparative molecular dynamics (MD) simulations (at 310, 350, 400, and 500 K) revealed that the thermal stability of PhyA from Aspergillus niger (A. niger) is associated with its conformational rigidity. The most thermally sensitive regions were identified as loops 8 (residues 83-106), 10 (161174), 14 (224-230), 17 (306-331), and 24 (442-444), which are present on the surface of the protein. It was observed that solvent-exposed loops denature before or show higher flexibility than buried residues. We observed that PhyA begins to unfold at loops 8 and 14, which further extends to loop 24 at the C-terminus. The intense movement of loop 8 causes the helix H2 and beta-sheet B3 to fluctuate at high temperature. The high flexibility of the H2, H10, and H12 helices at high temperature resulted in complete denaturation. The high mobility of loop 14 easily transfers to the adjacent helices H7, H8, and H9, which fluctuate and partially unfold at high temperature (500 K). It was also observed that the salt bridges Asp110-Lys149, Asp205-Lys277, Asp335-Arg136, Asp416-Arg420, and Glu387-Arg400 are important influences on the structural stability but not the thermostability, as the lengths of these salt bridges did not increase with rising temperature. The salt bridges Glu125-Arg163, Asp299-Arg136, Asp266-Arg219, Asp339-Lys278, Asp335-Arg136, and Asp424-Arg428 are all important for thermostability, as the lengths of these bridges increased dramatically with increasing temperature. Here, for the first time, we have computationally identified the thermolabile regions of PhyA, and this information could be used to engineer novel thermostable phytases. Numerous homologous phytases of fungal as well as bacterial origin are known, and these homologs show high sequence similarity. Our findings could prove useful in attempts to increase the thermostability of homologous phytases via protein engineering.
Keywords: Conformational dynamics; Molecular dynamics simulations; PhytaseA; Structurally weak regions; Thermostability

Investigation of phosphoproteome in RAGE signaling - Batkulwar, Kedar B.; Bansode, Sneha B.; Patil, Gouri V.; Godbole, Rashmi K.; Kazi, Rubina S.; Chinnathambi, Subashchandrabose; Shanmugam, Dhanasekaran; Kulkarni, Mahesh J. (Proteomics, 2015)
The receptor for advanced glycation end products (RAGE) is one of the most important proteins implicated in diabetes, cardiovascular diseases, neurodegenerative diseases, and cancer. It is a pattern recognition receptor by virtue of its ability to interact with multiple ligands, RAGE activates several signal transduction pathways through involvement of various kinases that phosphorylate their respective substrates. Only few substrates have been known to be phosphorylated in response to activation by RAGE (e.g., nuclear factor kappa B); however, it is possible that these kinases can phosphorylate multiple substrates depending upon their expression and localization, leading to altered cellular responses in different cell types and conditions. One such example is, glycogen synthase kinase 3 beta which is known to phosphorylate glycogen synthase, acts downstream to RAGE, and hyperphosphorylates microtubule-associated protein tau causing neuronal damage. Thus, it is important to understand the role of various RAGE-activated kinases and their substrates. Therefore, we have reviewed here the details of RAGE-activated kinases in response to different ligands and their respective phosphoproteome. Furthermore, we discuss the analysis of the data mined for known substrates of these kinases from the PhosphoSitePlus (http://www.phosphosite.org) database, and the role of some of the important substrates involved in cancer, diabetes, cardiovascular diseases, and neurodegenerative diseases. In summary, this review provides information on RAGE-activated kinases and their phosphoproteome, which will be helpful in understanding the possible role of RAGE and its ligands in progression of diseases.
Keywords: Cell biology; Disease; Glycation; Kinase; Phosphoproteome; RAGE

Iron superoxide dismutases in eukaryotic pathogens: new insights from apicomplexa and trypanosoma structures - Phan, Isabelle Q. H.; Davies, Douglas R.; Moretti, Nilmar Silvio; Shanmugam, Dhanasekaran; Cestari, Igor; Anupama, Atashi; Fairman, James W.; Edwards, Thomas E.; Stuart, Kenneth; Schenkman, Sergio; Myler, Peter J. (Acta Crystallographica Section F-Structural Biology Communications, 2015)
Prior studies have highlighted the potential of superoxide dismutases as drug targets in eukaryotic pathogens. This report presents the structures of three iron-dependent superoxide dismutases (FeSODs) from Trypanosoma cruzi, Leishmania major and Babesia bovis. Comparison with existing structures from Plasmodium and other trypanosome isoforms shows a very conserved overall fold with subtle differences. In particular, structural data suggest that B. bovis FeSOD may display similar resistance to peroxynitrite-mediated inactivation via an intramolecular electron-transfer pathway as previously described in T. cruzi FeSOD isoform B, thus providing valuable information for structure-based drug design. Furthermore, lysine-acetylation results in T. cruzi indicate that acetylation occurs at a position close to that responsible for the regulation of acetylation-mediated activity in the human enzyme.
Keywords: Apicomplexa; iron superoxide dismutase; Trypanosoma

Isolation, characterization and antifungal docking studies of wortmannin isolated from penicillium radicum - Singh, Vineeta; Praveen, Vandana; Tripathi, Divya; Haque, Shafiul; Somvanshi, Pallavi; Katti, S. B.; Tripathi, C. K. M. (Scientific Reports, 2015)
During the search for a potent antifungal drug, a cell-permeable metabolite was isolated from a soil isolate taxonomically identified as Penicillium radicum. The strain was found to be a potent antifungal agent. Production conditions of the active compound were optimized and the active compound was isolated, purified, characterized and identified as a phosphoinositide 3-kinase (PI3K) inhibitor, commonly known as wortmannin (Wtmn). This is very first time we are reporting the production of Wtmn from P. radicum. In addition to its previously discovered anticancer properties, the broad spectrum antifungal property of Wtmn was re-confirmed using various fungal strains. Virtual screening was performed through molecular docking studies against potential antifungal targets, and it was found that Wtmn was predicted to impede the actions of these targets more efficiently than known antifungal compounds such as voriconazole and nikkomycin i.e. 1) mevalonate-5-diphosphate decarboxylase (1FI4), responsible for sterol/isoprenoid biosynthesis; 2) exocyst complex component SEC3 (3A58) where Rho-and phosphoinositide-dependent localization is present and 3) Kre2p/Mnt1p a Golgi alpha1,2-mannosyltransferase (1S4N) involved in the biosynthesis of yeast cell wall glycoproteins). We conclude that Wtmn produced from P. radicum is a promising lead compound which could be potentially used as an efficient antifungal drug in the near future after appropriate structural modifications to reduce toxicity and improve stability.

Landscapes of membrane protein interactions from high-throughput MD simulations using the daft approach - Wassenaar, Tsjerk A.; Pluhackova, Kristyna; Moussatova, Anastassiia; Sengupta, Durba; Marrink, Siewert-Jan; Tieleman, D. Peter; Boeckmann, Rainer A. (Biophysical Journal, 2015)
59th Annual Meeting of the Biophysical-Society, Baltimore, MD, FEB 07-11, 2015

Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method - Ghosh, Aryya; Pal, Sourav; Vaval, Nayana (Journal of Chemical Physics, 2015)

Ligand-, base-, co-catalyst-free copper fluorapatite (CuFAP) as a versatile, ecofriendly, heterogeneous and reusable catalyst for an efficient homocoupling of arylboronic acid at ambient reaction conditions - Mulla, Shafeek Abdul Rashid; Chavan, Santosh S.; Pathan, Mohsinkhan Y.; Inamdar, Suleman M.; Shaikh, Taufeekaslam M. Y. (RSC Advances, 2015)
This paper describes the first report in which copper species containing copper fluorapatite (CuFAP) acts as a versatile, eco-friendly, recyclable, heterogeneous catalyst for an efficient synthesis of symmetric biaryls from the homo-coupling of arylboronic acids in methanol solvent at ambient reaction conditions. The developed protocol is ligand-, base-, and co-catalyst-free, sustainable, mild, inexpensive, and compatible with a wide range of aromatic/heterocyclic boronic acids and provides the corresponding products in excellent yields without purification. The catalyst was easily recovered from the reaction mixture and reused several times without loss of activity.

Long chain branched impact copolymer of polypropylene: microstructure and rheology - Chikhalikar, Kalyani; Deshpande, Anushree; Pol, Harshawardhan; Dhoble, Deepa Arun; Jha, Saroj; Jadhav, Kishor; Mahajan, Sunil; Ahmad, Zubair; Kulkarni, Surendra; Gupta, Surendra; Lele, Ashish K. (Polymer Engineering and Science, 2015)
A biphasic impact copolymer of polypropylene (ICP) was modified with peroxide by reactive extrusion process resulting in reduced melt flow index, improved melt strength, and higher die swell. The polymers were for the first time subjected to systematic rheological and microstructural characterization in an effort to understand their structure-property relations. In shear rheological tests, the modified ICP displayed higher flow activation energy, reduced values of loss tangent and nearly equal frequency dependence of storage and loss modulli. The modified ICP also showed strain hardening behaviour in uniaxial extensional rheology and higher crystallization temperature in differential scanning calorimetry (DSC). All these are definitive indications of the presence of long chain branches (LCB). Fitting the rheological data of modified ICPs with the eXtended Pom Pom (XPP) model indicated the presence of LCB on the higher molecular weight fraction in the polymer, a result which was corroborated with multi-detector high temperature gel permeation chromatography (HT-GPC). More importantly, the matrix and rubber phases of the ICP were separately characterized for presence of long chain branching by rheology, DSC and HT-GPC. The results indicate that while LCB existed in the matrix phase, microgels were present in both phases indicating that the reaction with peroxide occurred in both phases. POLYM. ENG. SCI., 55:1463-1474, 2015. (c) 2014 Society of Plastics Engineers

Low-temperature sintering and microwave dielectric properties of Zn2SiO4 ceramic added with crystalline zinc borate - Chaware, Varsha; Deshmukh, Ravindra; Sarode, Chetan; Gokhale, Suresh; Phatak, Girish (Journal of Electronic Materials, 2015)
The physical and dielectric properties of composites of known microwave materials, Zn2SiO4 and Zn3B2O6, prepared by solid-state reaction, were investigated with the purpose of developing a low-loss dielectric material for low-temperature co-fired ceramic applications. An off-stoichiometric phase of Zn2SiO4 with extra SiO2 was used to avoid the occurrence of unreacted ZnO. During sintering, zinc borate was found to partially react with residual SiO2 to form Zn2SiO4. The residual zinc borate was converted to a boron-rich glassy phase which helped to reduce the sintering temperature of the composite. Good relative sintering density (> 90%) at temperatures below the melting temperature of zinc borate is indicative of a sintering mechanism of diffusion-based mass transfer. Composites containing 15 wt.% zinc borate, 2.5 wt.% lithium carbonate and 20 wt.% zinc borate in zinc silicate had dielectric constants of 6.8 and 6.1, quality factors (Qxf) of 48,800 and 94,300 GHz when sintered at 900A degrees C and 950A degrees C, respectively. These quality factor results are close to the best values reported for zinc silicate at these sintering temperatures.
Keywords: dielectric constant; LTCC; quality factor; sintering density; zinc borate; zinc silicate

Mechanistic insight into the biomilling of goethite (alpha-FeO(OH)) nanorods using the yeast Saccharomyces cerevisiae - Sharan, Chandrashekhar; Khandelwal, Puneet; Poddar, Pankaj (RSC Advances, 2015)
Since the last decade, eco-friendly routes for the synthesis of nanostructured materials of various types and functionalities have been a topic of enormous interest in the field of nanotechnology. The primary work in this field started with the `bottom-up' microbial synthesis of nanoparticles, however, the bioleaching potential of microbes was initially overlooked in this research. The bioleaching process is useful especially where the synthesis of particles with size < 10 nm is challenging. In the present work, the mechanistic insight of biomilling for a gradual transformation of anisotropic alpha-FeO(OH) rod-shaped particles into isotropic nanoparticles below 10 nm size has been explored using detailed UV-vis spectroscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopic studies which suggest that the aquo group present at the alpha-FeO(OH) surface may provide the site for interaction with carboxyl ions of protein molecules which results in the formation of a stable coordination compound with Fe3+ ions. This will create a new Fe3+ ion on the surface of the lattice which leads to the repetition of the process of protein complexation with Fe3+ ions and dissociation of the complex from the lattice that causes the fragmentation of bigger nanoparticles into protein functionalized smaller nanoparticles.

Mechanistic understanding of rapid gelation of silk fibroin using a biosurfactant – sophorolipid - Dubey, Parul; Nawale, Laxman; Sarkar, Dhiman; Nisal, Anuya; Prabhune, Asmita (National Science Day, At CSIR-NCL, 2015)
3D polymeric hydrogels find use in biomedical applications as scaffolds and drug delivery vehicle • Silk fibroin a structural protein is a promising candidate (excellent thermo-mechanicals, biocompatibility, biodegradability) • Sophorolipid (SL)-a biosurfactant is known to exhibit antimicrobial, anti cancerous and cell differentiating. • Use of SL as gelling agent can enhance the applicability of SF hydrogels • SF-SL scaffolds obtained by lyophilization of hydrogels can find application in tissue regeneration

MegaMiner: a tool for lead identification through text mining using chemoinformatics tools and cloud computing environment - Karthikeyan, Muthukumarasamy; Pandit, Yogesh; Pandit, Deepak; Vyas, Renu (Combinatorial Chemistry & High Throughput Screening, 2015)
Virtual screening is an indispensable tool to cope with the massive amount of data being tossed by the high throughput omics technologies. With the objective of enhancing the automation capability of virtual screening process a robust portal termed MegaMiner has been built using the cloud computing platform wherein the user submits a text query and directly accesses the proposed lead molecules along with their drug-like, lead-like and docking scores. Textual chemical structural data representation is fraught with ambiguity in the absence of a global identifier. We have used a combination of statistical models, chemical dictionary and regular expression for building a disease specific dictionary. To demonstrate the effectiveness of this approach, a case study on malaria has been carried out in the present work. MegaMiner offered superior results compared to other text mining search engines, as established by F score analysis. A single query term `malaria' in the portlet led to retrieval of related PubMed records, protein classes, drug classes and 8000 scaffolds which were internally processed and filtered to suggest new molecules as potential anti-malarials. The results obtained were validated by docking the virtual molecules into relevant protein targets. It is hoped that MegaMiner will serve as an indispensable tool for not only identifying hidden relationships between various biological and chemical entities but also for building better corpus and ontologies.
Keywords: Chemoinformatics; cloud computing; malaria; text mining; virtual screening

Mesoporous TUD-1 supported indium oxide nanoparticles for epoxidation of styrene using molecular O-2 - Rahman, Sumbul; Farooqui, Saleem A.; Rai, Aditya; Kumar, Rawesh; Santra, Chiranjit; Prabhakaran, Vinod C.; Bhadu, Gopala Ram; Sen, Debasis; Mazumder, S.; Maity, Sudip; Sinha, Anil K.; Chowdhury, Biswajit (RSC Advances, 2015)
Activation of molecular O-2 by metal or metal oxide nanoparticles is an area of recent research interest. In this work, for the first time, we report that indium oxide nanoparticles of <3 nm size dispersed on mesoporous silica (TUD-1) can activate molecular O-2 and produce styrene epoxide with a selectivity of 60% and styrene conversion around 25% under mild conditions. It is found that neither indium oxide nor TUD-1 themselves respond to the styrene epoxidation reaction. The computational studies provide evidence that an oxygen molecule is highly polarized when it is located near the interface of both surfaces. The kinetic study shows that the reaction is of pseudo-first order and that the activation energy for styrene conversion is 12.138 kJ mol(-1). The catalysts are recyclable for up to four regeneration steps, with the styrene conversion and styrene epoxide selectivity almost unchanged.

Metabolic profiling of chickpea-Fusarium interaction identifies differential modulation of disease resistance pathways - Kumar, Yashwant; Dholakia, Bhushan B.; Panigrahi, Priyabrata; Kadoo, Narendra Y.; Giri, Ashok P.; Gupta, Vidya S. (Phytochemistry, 2015)
Chickpea is the third most widely grown legume in the world and mainly used as a vegetarian source of human dietary protein. Fusarium wilt, caused by Fusarium oxysporum f. sp. ciceri (Foc), is one of the major threats to global chickpea production. Host resistance is the best way to protect crops from diseases; however, in spite of using various approaches, the mechanism of Foc resistance in chickpea remains largely obscure. In the present study, non-targeted metabolic profiling at several time points of resistant and susceptible chickpea cultivars using high-resolution liquid chromatography-mass spectrometry was applied to better understand the mechanistic basis of wilt resistance or susceptibility. Multivariate analysis of the data (OPLS-DA) revealed discriminating metabolites in chickpea root tissue after Foc inoculation such as flavonoids, isoflavonoids, alkaloids, amino acids and sugars. Foc inoculated resistant plants had more flavonoids and isoflavonoids along with their malonyl conjugates. Many antifungal metabolites that were induced after Foc infection viz, aurantion-obstine beta-glucosides and querecitin were elevated in resistant cultivar. Overall, diverse genetic and biochemical mechanisms were operational in the resistant cultivar for Foc defense as compared to the susceptible plant. The resistant chickpea plants employed the above-mentioned metabolic pathways as potential defense strategy against Foc. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Chickpea; Fusarium wilt; LC-MS; Metabolomics; OPLS-DA; Phytoalexin

Metal-free regioselective C-3 acetoxylation of N-substituted indoles: crucial impact of nitrogen-substituent - Soni, Vineeta; Patel, Ulhas N.; Punji, Benudhar (RSC Advances, 2015)
A metal-free method for the regioselective C-3 acetoxylation of the N-substituted indoles with PhI(OAc)(2) is described under mild reaction conditions. This method tolerates a broad range of functional groups with moderate to good yields. The pi-electron-deficient aryl-substituents on the N-atom of indoles and the acidic reaction medium remarkably favor C-3 acetoxylation.

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

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

Modeling hysteresis during crystallization and dissolution: application to a paracetamol-ethanol system - Pandit, Ajinkya V.; Ranade, Vivek V. (Industrial & Engineering Chemistry Research, 2015)
Crystallization and dissolution processes are of great scientific and commercial interest. Significant efforts have been made in the past to develop mathematical models to describe these processes. In this work, observed hysteresis in particle counts during the crystallization and dissolution processes was used to develop and to test the mathematical models of crystallization and dissolution. Crystallization and dissolution experiments were performed with a system of paracetamol and ethanol. An undersaturated solution was first cooled at a particular rate causing crystallization and crystal growth. The solution was then reheated at the same rate to completely dissolve the generated particles. The particle counts and particle size distribution were measured online using a focus beam reflectance measurement (FBRM) probe. A hysteresis was observed in particle counts with respect to the solution temperature. It was also observed that this hysteresis was affected by the applied heating/cooling rates (0.3, 0.5, and 0.7 K/min) for of the solution. A systematic modeling framework based on the population balance equation (PBE) is developed for quantitatively capturing this hysteresis and the influence of cooling/heating rate on the hysteresis curve. A two-level approach was developed to simulate hysteresis: (a) PBE was solved using computationally efficient method of moments for the crystallization stage. This step was used to efficiently estimate values of parameters appearing in the model equations. (b) PBEs describing crystallization and dissolution were then solved using high resolution finite volume (HRFV) scheme coupled with the moving pivot method. The simulated hysteresis curve showed good agreement with the experimental data. Though simulated results over predicted the average particle (by,similar to 131%), the models were successful in qualitatively explaining the counterintuitive trends observed as the average particle size was tracked with time. The framework was thus shown to be a reliable and robust framework to model crystallization and dissolution processes. The developed approach, models, and results will be useful for simulating industrially relevant crystallization dissolution processes.

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 Fe-complex as a catalyst probe for in-gel visual detection of proteins via signal amplification - Kumari, Sushma; Panda, Chakadola; Mazumdar, Shyamalava; Sen Gupta, Sayam (Chemical Communications, 2015)
We report the use of a molecular peroxidase mimic biuret-Fe-TAML for chemoselective labeling of proteins and the subsequent visual detection (<0.1 pmoles) of the conjugate in a polyacrylamide gel by catalytic signal amplification. Use of this probe in activity based protein profiling (ABPP) of serine proteases is also demonstrated.

Mono- and binuclear palladacycles via regioselective C-H bond activation: syntheses, mechanistic insights and catalytic activity in direct arylation of azoles - Pandey, Dilip K.; Khake, Shrikant M.; Gonnade, Rajesh G.; Punji, Benudhar (RSC Advances, 2015)
{Regioselective C-H bond palladation of the hybrid pincer-type ligands, 3-R2PO-C6H4-1-(CH2NPr2)-Pr-i [(POCNiPr2)-P-R2-H; R = Ph (1a)

Multifunctional polyaniline-tin oxide (PANI-SnO2) nanocomposite: synthesis, electrochemical, and field emission investigations - Patil, Sandip S.; Harpale, Kashmira V.; Koiry, Shankar P.; Patil, Kashinath R.; Aswal, Dinesh K.; More, Mahendra A. (Journal of Applied Polymer Science, 2015)
Synthesis of PANI-SnO2 nanocomposite has been performed using a simple two step chemical oxidative polymerization route. The structural, morphological and chemical properties of the as-synthesized PANI-SnO2 nanocomposite have been revealed by various characterization techniques such as SEM, TEM, XRD, FTIR, and XPS. Interestingly the as-synthesized PANI-SnO2 nanocomposite exhibits supercapacitance value of 721 F g(-1) with energy density 64 Wh kg(-1), which is noticed to be higher than that of pristine SnO2 and PANI nanostructures. Furthermore, the galvanostatic charge-discharge characteristics revealed pseudocapacitive nature of the PANI-SnO2 nanocomposite. The estimated values of charge transfer resistance and series resistance estimated from the Nyquist plot are found to be lower. Along with the supercapacitive nature, PANI-SnO2 nanocomposite showed promising field emission behavior. The threshold field, required to draw emission current density of 1 A/cm(2), is observed to be 0.90 V/m and emission current density of 1.2 mA/cm(2) has been drawn at applied field of approximate to 2.6 V/m. The emission current stability investigated at preset values of 0.02 and 0.1 mA/cm(2) is observed to be fairly stable over duration of more than 3 h. The enhanced supercapacitance values, as well as, the promising field emission characteristics are attributed to the synergic effect of SnO2 nanoparticles and PANI nanotubes. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41401.
Keywords: conducting polymers; Electrochemistry; nanostructured polymers; surfaces and interfaces

Nanostructured 2D MoS2 honeycomb and hierarchical 3D CdMoS4 marigold nanoflowers for hydrogen production under solar light - Kadam, Sunil R.; Late, Dattatray J.; Panmand, Rajendra P.; Kulkarni, Milind V.; Nikam, Latesh K.; Gosavi, Suresh W.; Park, Chan J.; Kale, Bharat B. (Journal of Materials Chemistry A, 2015)
Unique two dimensional (2D) honeycomb layered MoS2 nanostructures and hierarchical 3D marigold nanoflowers of CdMoS4 were designed using a template free and facile solvothermal method. The MoS2 structure is depicted with a sheet like morphology with lateral dimensions of 5-10 mu m and a thickness of similar to 200 nm and a honeycomb nanostructure architecture produced via the self-assembling of vertically grown thin hexagonal nanosheets with a thickness of 2-3 nm. The 3D CdMoS4 marigold nanoflower architecture comprised thin nanopetals with lateral dimensions of 1-2 mu m and a thickness of a few nm. The CdMoS4 and MoS2 structures displayed hydrogen ( H-2) production rates of 25 445 and 12 555 mu mol h(-1) g(-1), respectively. The apparent quantum yields of hydrogen production were observed to be 35.34% and 17.18% for CdMoS4 and MoS2, respectively. The 3D nanostructured marigold flowers of CdMoS4 and honeycomb like 2D nanostructure of MoS2 were responsible for higher photocatalytic activity due to inhibition of the charge carrier recombination. The prima facie observation of H-2 production showed that the ternary semiconductor confers enhanced photocatalytic activity for H-2 generation due to its unique structure. Such structures can be designed and implemented in other transition metal dichalcogenide based ternary materials for enhanced photocatalytic and other applications.

New atom transfer radical polymerization initiator based on phenolphthalein for the synthesis of bis-allyloxy functionalized polystyrene macromonomers - Patil, Sachin S.; Menon, Shamal K.; Wadgaonkar, Prakash P. (Polymer International, 2015)
A new atom transfer radical polymerization (ATRP) initiator, namely 2-(1,1-bis(4-(allyloxy)phenyl)-3-oxoisoindolin-2-yl)ethyl 2-bromo-2-methylpropanoate, was synthesized starting from phenolphthalein, a commercially available and an inexpensive chemical. Well- defined bis-allyloxy functionalized polystyrene macromonomers (M-n,M-GPC 4800-11 700gmol(-1)) with controlled molecular weight and narrow molecular weight distribution (1.05-1.09) were synthesized using ATRP by varying the monomer to initiator feed ratio. The presence of allyloxy functionality on polystyrene was confirmed by Fourier transform infrared and H-1 NMR spectroscopy. A kinetic study of polymerization revealed pseudo-first-order kinetics with respect to monomer consumption. Initiator efficiency was found to be in the range 0.80-0.95. Matrix-assisted laser desorption ionization time of flight spectra showed a narrow molecular weight distribution with control over the molecular weight. The reactivity of the allyloxy groups on polystyrene was successfully demonstrated by quantitative photochemical thiol-ene click reaction with benzyl mercaptan as the model thiol reagent. Furthermore, the thiol-ene click reaction was exploited to introduce other reactive functional groups such as hydroxyl and carboxyl by reaction of ,-bis-allyloxy functionalized polystyrene with 2-mercaptoethanol and 3-mercaptopropionic acid, respectively. (c) 2014 Society of Chemical Industry
Keywords: atom transfer radical polymerization; bis-allyloxy functionalized polystyrene; functional initiator; phenolphthalein; thiol-ene click reaction

New class of bacterial quorum sensing antagonists: glycomonoterpenols synthesized using linalool and alpha terpineol - Mukherji, Ruchira; Prabhune, Asmita (World Journal of Microbiology & Biotechnology, 2015)
With increasing burden of antibiotic resistant microorganism search for newer drug targets and potent drug molecules is a never ending scenario. Quorum sensing (QS), the phenomenon of bacterial cross-talk, is one such target that has captured the attention of many and has been touted as the future of new age antimicrobials. Quorum sensing has the potential to regulate a plethora of bacterial virulence phenotypes and search of molecules with powerful quorum sensing inhibitory (QSI) capacity are underway. Monoterpene alcohols like linalool and alpha terpineol have been shown to possess antimicrobial and anti-biofilm activity. However in this article we attempt to bring forth a new class of compounds, glycomonoterpenols, derived from monoterpenoids alcohols. These glycomonoterpenols have been synthesized using Candida bombicola ATCC 22214 by feeding the cells with linalool and alpha terpineol respectively as substrates in 10 % glucose, production medium. The advantage of these molecules over their parent compound is their additional surfactant like property, increased solubility and enhanced QSI potential. A variety of gram-negative bacteria capable of elaborating quorum sensing mediated phenotypes have been selected and both these glycoterpenoid derivatives have been shown to possess strong anti-QS activity.
Keywords: Alpha-terpineol; Glycomonoterpenols; Linalool; Pseudomonas aeruginosa; Quorum sensing inhibition

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

New scheme for perturbative triples correction to (0,1) sector of Fock space multi-reference coupled cluster method: Theory, implementation, and examples - Dutta, Achintya Kumar; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2015)
We propose a new elegant strategy to implement third order triples correction in the light of many-body perturbation theory to the Fock space multi-reference coupled cluster method for the ionization problem. The computational scaling as well as the storage requirement is of key concerns in any many-body calculations. Our proposed approach scales as N-6 does not require the storage of triples amplitudes and gives superior agreement over all the previous attempts made. This approach is capable of calculating multiple roots in a single calculation in contrast to the inclusion of perturbative triples in the equation of motion variant of the coupled cluster theory, where each root needs to be computed in a state-specific way and requires both the left and right state vectors together. The performance of the newly implemented scheme is tested by applying to methylene, boron nitride (B2N) anion, nitrogen, water, carbon monoxide, acetylene, formaldehyde, and thymine monomer, a DNA base. (C) 2015 AIP Publishing LLC.

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

N-Heterocyclic carbene-catalyzed diastereoselective synthesis of β-lactone-fused cyclopentanes using homoenolate annulation reaction - Mukherjee, Subrata; Mondal, Santigopal; Patra, Atanu; Gonnade, Rajesh G.; Biju, Akkattu T. (Chemical Communications, 2015)
NHC-catalyzed annulation of enals with 2-enoylpyridines or 2-enoylpyridine N-oxides leading to the diastereoselective synthesis of β-lactone-fused cyclopentanes is reported. The reaction proceeds via the generation of homoenolate equivalent intermediates and tolerates a broad range of functional groups.

NiS1.97: a new efficient water oxidation catalyst for photoelectrochemical hydrogen generation - Bhosale, Reshma; Kelkar, Sarika A.; Parte, Golu; Fernandes, Rohan; Kothari, Dushyant; Ogale, Satishchandra (ACS Applied Materials & Interfaces, 2015)
NiS1.97, a sulfur-deficient dichalcogenide, in nanoscale form, is shown to be a unique and efficient photoelectrochemical (PEC) catalyst for H-2 generation by water splitting. Phase pure NiS1.97 nanomaterial is obtained by converting nickel oxide into sulfide by controlled sulfurization method, which is otherwise difficult to establish. The defect states (sulfur vacancies) in this material increase the carrier density and in turn lead to favorable band line-up with respect to redox potential of water, rendering it to be an effective photoelectrochemical catalyst. The material exhibits a remarkable PEC performance of 1.25 mA/cm(2) vs NHE at 0.68 V in neutral pH, which is almost 1000 times superior as compared with that of the stoichiometric phase of NiS2. The latter is well-known to be a cocatalyst but not as a primary PEC catalyst.
Keywords: dichlacogenide; Faradaic efficiency; Hydrogen generation; NiS1.97; nonstoichiometric; photoelectrochemical catalyst; sulfurization

Nitrogen-induced surface area and conductivity modulation of carbon nanohorn and its function as an efficient metal-free oxygen reduction electrocatalyst for anion-exchange membrane fuel cells - Unni, SreeKuttan M.; Bhange, Siddheshwar N.; Illathvalappil, Rajith; Mutneja, Nisha; Patil, Kasinath R.; Kurungot, Sreekumar (SMALL, 2015)
Nitrogen-doped carbon morphologies have been proven to be better alternatives to Pt in polymer-electrolyte membrane (PEM) fuel cells. However, efficient modulation of the active sites by the simultaneous escalation of the porosity and nitrogen doping, without affecting the intrinsic electrical conductivity, still remains to be solved. Here, a simple strategy is reported to solve this issue by treating single-walled carbon nanohorn (SWCNH) with urea at 800 degrees C. The resulting nitrogen-doped carbon nanohorn shows a high surface area of 1836 m(2) g(-1) along with an increased electron conductivity, which are the pre-requisites of an electro catalyst. The nitrogen-doped nanohorn annealed at 800 degrees C (N-800) also shows a high oxygen reduction activity (ORR). Because of the high weight percentage of pyridinic nitrogen coordination in N-800, the present catalyst shows a clear 4-electron reduction pathway at only 50 mV overpotential and 16 mV negative shift in the half-wave potential for ORR compared to Pt/C along with a high fuel selectivity and electrochemical stability. More importantly, a membrane electrode assembly (MEA) based on N-800 provides a maximum power density of 30 mW cm(-2) under anion-exchange membrane fuel cell (AEMFC) testing conditions. Thus, with its remarkable set of physical and electrochemical properties, this material has the potential to perform as an efficient Pt-free electrode for AEMFCs.

Novel one-pot multi-component synthesis of 3,3 `-disubstituted oxindole and spirooxindole scaffolds via Sn-catalyzed C(sp(3))-H functionalization of azaarenes by sequential Knoevenagel-Michael-cyclization reaction - Chavan, Santosh S.; Pathan, Mohsinkhan Y.; Thorat, Shridhar H.; Gonnade, Rajesh G.; Mulla, Shafeek Abdul Rashid (RSC Advances, 2015)
Sn-catalyzed C(sp(3))-H bond functionalization of 2-methyl azaarenes/2-(azaaryl)methanes has been achieved for the first time in a one-pot multi-component reaction with isatin and active methylene compounds via tandem sequential Knoevenagel-Michael-intramolecular C-N cyclization. This strategy provides new cost-effective access to potent and biologically/medicinally important spirooxindoles/3,3'-disubstituted 2-oxindoles in good to excellent yields.

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 step synthesis of ethyl levulinate biofuel by ethanolysis of renewable furfuryl alcohol over hierarchical zeolite catalyst - Nandiwale, Kakasaheb Y.; Pande, Ashwini M.; Bokade, Vijay V. (RSC Advances, 2015)
Ethanolysis of renewable furfuryl alcohol (FAL) to ethyl levulinate (EL) biofuel over various zeolites viz. H-ZSM-5 (microporous, medium pore), Hierarchical-HZ-5 (combination of micro-and meso pore), H-Beta (microporous, large pore) and Ultra Stable Y (USY, microporous, large pore) was studied in detail. To the best of our knowledge, probably for the first time, Hierarchical-HZ-5 synthesized by desilication post-treatment has been employed as a heterogeneous catalyst for ethanolysis of FAL. The synthesized catalysts were characterized by powder X-ray diffraction (PXRD), temperature programmed NH3 desorption (TPAD), Energy dispersive X-ray analysis (EDAX), etc. Response surface methodology (RSM) with Box-Behnken experimental design (BBD) was used to investigate the influence of three crucial process variables of ethanolysis such as ethanol to FAL molar ratio, percent catalyst loading and reaction temperature on EL yield. The optimization tool of design expert software was employed to obtain the optimum reaction parameters for FAL ethanolysis over Hierarchical-HZ-5 catalyst. Three intermediates of FAL ethanolysis reaction such as, ethoxymethylfuran (EMF), 4,5,5-triethoxypentan-2-one and diethyl ether (DEE) have been identified and quantified from the product mixture with the aid of Gas Chromatography-Mass Spectroscopy (GC-MS). Hierarchical-HZ-5 was found to be a potential catalyst for ethanolysis of FAL with 73% EL yield and 26% EMF yield at optimized process parameters.

Optimisation of parameters affecting the performance of single compartment CEDI unit - Thorat, Prathamesh P.; Desale, G. R.; Gajjal, S. Y.; Patil, Sagar R. (1ST International Conference on Computing Communication Control and Automation ICCUBEA 2015, 2015)
The present work describes the production of the ultrapure water using Continuous Electro-deionization (CEDI) method. TheCEDI unit consist of ion exchange membranes, Mixed Bed-12 (MB-12) ion exchange resin and electrodes to remove ion impurities from feed water. The product water from the RO unit is supplied to the CEDI unit. The Quality of the ultra-pure water is determined by the amount of ions present in the water. Higher quality of Ultra-pure water is obtained when the maximum number of ions is transferred through the membranes. The Parameters affecting the performance of the CEDI unit are identified and optimized for maximum ions exchange. Inorder to reduce the number of experimentsTaguchi method was used for optimisation of operating parameters. An orthogonal L array (three factor and three level) was employed to evaluate the effect of feed concentration (35,40and 45 ppm), Flow rate (8, 9 and 10 LPH) and voltage (22, 23, 24 volts). Thus it was observed that increasing the applied voltage anddecreasing the waterflow rateincreases the number of ions transfers through the membrane. However, decreasing water flow rate has certain limits as it decreases the production capacity of the unit. Also it is observed that decreasing the ions in the feed water decreases the overall transfer of ions.
Keywords: Continuous Electro-deionization; Ion Exchange membranes; Optimisation; Taguchi method; Ultrapure Water

Overexpression of squalene synthase in withania somnifera leads to enhanced withanolide biosynthesis - Patel, Neha; Patel, Parth; Kendurkar, Shuchishweta V.; Thulasiram, Hirekodathakallu V.; Khan, Bashir Mohammad (Plant Cell Tissue and Organ Culture, 2015)
Genetic engineering of secondary metabolic pathways is an emerging area of research for production and improvement of natural products in plant biotechnology. Here, we describe a systematic approach to manipulate a key regulatory step of isoprenoid biosynthetic pathway in Withania somnifera to study its effect on withanolide production. We generated T-0 W. somnifera plants overexpressing squalene synthase (WsSQS) by Agrobacterium tumefaciens mediated transformation, which were analyzed by Gus biochemical assay and PCR of hygromycin phosphotransferase (hptII) and WsSQS. qRT-PCR analyses of various transformed tissues indicated 2-5 fold increase in WsSQS transcripts in both T-0 and T-1 generations. The tissue specific protein expression studies revealed 2-3 fold increase in WsSQS, which was further confirmed by enzyme activity. These observations were corroborated with the 1.5-2 fold increase in total withanolide content of the transformed tissues. However, in leaf tissue, the levels of Withaferin A and Withanolide A increased significantly up to 4-4.5 fold. These findings demonstrate genetic engineering of isoprenoid pathway in W. somnifera resulting in enhanced production of withanolides, and also provide insights into such metabolic pathways for their manipulation to improve the pharmacological content of different medicinally important plants.
Keywords: Agrobacterium tumefaciens; Solanaceae; Squalene synthase; Withania somnifera; Withanolides

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.

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.

Oxone-acetone mediated syn-dioxygenation of benzo-fused olefins - Phatake, Ravindra S.; Ramana, Chepuri V. (Tetrahedron Letters, 2015)
The oxone-acetone combination well established for olefin epoxidation has been demonstrated to be a practical reagent for the syn-dioxygenation (resulting in 1,3-dioxolanes) of indenes and dihydronaphthalenes. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Dihydronaphthalene; Dioxygenation; Indene; Oxone

Oxone-acetone mediated wacker-type oxidation of benzo-fused olefins - Phatake, Ravindra S.; Ramana, Chepuri V. (Tetrahedron Letters, 2015)
Herein we disclose a novel application of the oxone-acetone combination for the Wacker-type oxidation of indenes and dihydronaphthalenes leading, respectively, to indan-2-ones and 2-tetralones. The amount of the base employed in the reaction seems to switch the reaction path from dioxygenation to Wacker-type oxidation. Control experiments suggest that the reaction is not proceeding via the epoxide route and also that there is no role of trace amounts of metals present in the reagents on the current oxidation. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Dihydronaphthalene; Indene; Oxone; Wacker oxidation

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.
International Conference of Computational Methods in Sciences and Engineering (ICCMSE), Kos, GREECE, OCT 03-08, 2010
Keywords: Dipole moment; Multi-reference; Triples

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

Perturbative order analysis of the similarity transformed hamiltonian in fock-space coupled cluster theory: difference energy and electric response properties - Bhattacharya, Debarati; Dutta, Achintya Kumar; Gupta, Jitendra; Pal, Sourav (Molecular Physics, 2015)
A perturbative analysis of the ground-state similarity transformed Hamiltonian and its effect on the various Fock-space coupled cluster (FSCC) sectors is presented through calculation of ionisation potential, electron affinity, excitation energies and response properties. Various truncation schemes of the effective Hamiltonian are presented with explicit form of the defining equations. Based on such a truncation, the approximate methods are labelled as FSCC(n), where n represents the correlation energy of the ionised, electron attached or excited states corrected at least up to nth order within coupled cluster singles and doubles scheme (CCSD). A lower scaling CC2 type of approach (abbreviated as FS-CC2) is compared against the group of FSCC(n) methods for energies. Electric response properties have been compared and contrasted for the two lower scaling methods: FSCC(2) and FS-CC2. The various truncated methods are tested for a number of small molecules. The results obtained from a range of truncated methods are compared against full FSCCSD calculations.
Keywords: electric response properties; Fock space; perturbative order; similarity transformed Hamiltonian

Possible correlation between bile salt hydrolysis and ahl deamidation: staphylococcus epidermidis RM1, a potent quorum quencher and bile salt hydrolase producer - Mukherji, Ruchira; Prabhune, Asmita (Applied Biochemistry and Biotechnology, 2015)
The aim of the present work was to isolate a bile salt hydrolase (BSH) producer from fermented soy curd and explore the ability of the BSH produced to cleave bacterial quorum sensing signals. Bacterial isolates with possible ability to deconjugate bile salts were enriched and isolated on De Man, Rogosa and Sharpe (MRS) medium containing 0.2 % bile salts. BSH-producing positive isolate with orange-pink-pigmented colonies was isolated and was identified as a strain of Staphylococcus epidermidis using biochemical and phylogenetic tools. S. epidermidis RM1 was shown to possess both potent BSH and N-acyl homoserine lactone (AHL) cleavage activity. Genetic basis of this dual-enzyme activity was explored by means of specific primers designed using S. epidermidis ATCC 12228 genome as template. It was observed that a single enzyme was not responsible for both the activity. Two different genetic elements corresponding to each of the enzymatic activity were successfully amplified from the genomic DNA of the isolate.
Keywords: AHL acylase; Bile salt hydrolase; CV026; Quorum quenching; Staphylococcus epidermidis

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

Preparation of Ni3S2 and Ni3S2-Ni nanosheets via solution based processes - Busupalli, Balanagulu; Date, Kalyani S.; Datar, Suwarna; Bhagavatula L. V. Prasad (Crystal Growth & Design, 2015)
An easy and convenient preparation of nanometer-thick sheets of Ni3S2 and Ni3S2–Ni from solution processed molecularly thin sheets of Ni-thiolates is described. Both the Ni3S2 and Ni3S2–Ni possessed sheet-like morphologies and displayed room temperature ferromagnetic characteristics. The ferromagnetic nature of these samples was also confirmed by MFM studies, and AFM/TEM investigations substantiated the sheet-like morphology of the samples.

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.

Protein ligand complex guided approach for virtual screening - Karthikeyan, Muthukumarasamy; Pandit, Deepak; Vyas, Renu (Combinatorial Chemistry & High Throughput Screening, 2015)
The target ligand association data is a rich source of information which is not exploited enough for drug design efforts in virtual screening. A java based open-source toolkit for Protein Ligand Network Extraction (J-ProLiNE) focused on protein-ligand complex analysis with several features integrated in a distributed computing network has been developed. Sequence alignment and similarity search components have been automated to yield local, global alignment scores along with similarity and distance scores. 10000 proteins with co-crystallized ligands from pdb and MOAD databases were extracted and analyzed for revealing relationships between targets, ligands and scaffolds. Through this analysis, we could generate a protein ligand network to identify the promiscuous and selective scaffolds for multiple classes of proteins targets. Using J-ProLiNE we created a 507 x 507 matrix of protein targets and native ligands belonging to six enzyme classes and analyzed the results to elucidate the protein-protein, protein-ligand and ligand-ligand interactions. In yet another application of the J-ProLiNE software, we were able to process kinase related information stored in US patents to construct disease-gene-ligand-scaffold networks. It is hoped that the studies presented here will enable target ligand knowledge based virtual screening for inhibitor design.
Keywords: Complexes; ligand; protein; scaffolds; sequences; similarity score; virtual screening

Proton transport mechanism of imidazole, triazole and phosphoric acid mixtures from ab initio molecular dynamics simulations - Pahari, Swagata; Roy, Sudip (Physical Chemistry Chemical Physics, 2015)
We performed first principles molecular dynamics simulations to elucidate the mechanism and role of 1,2,3-triazole in proton transport while it is mixed with phosphoric acid (PA) and a phosphoric acid imidazole mixture. PA doped imidazole based polymer acts as an efficient polyelectrolyte membrane for fuel cells. The conductivity of this membrane increases when triazole is added to the system. For the first time we performed ab initio molecular dynamics simulations of complex mixtures of PA, imidazole and triazole. We have quantitatively estimated the structural diffusion and vehicular motion of protons. We found that upon the addition of triazole in PA and the PA imidazole mixture, the structural diffusion of protons increases significantly. The mechanism of proton transport is different when triazole is added to the mixture. We have also identified two different paths for structural diffusion (constructive and non-constructive) that contribute to long and short range proton transport.

p-type NiO hybrid visible photodetector - Mallows, John; Planells, Miguel; Thakare, Vishal; Bhosale, Reshma; Ogale, Satishchandra; Robertson, Neil (ACS Applied Materials & Interfaces, 2015)
A novel hybrid visible-light photodetector was created using a planar p-type inorganic NiO layer in a junction with an organic electron acceptor layer. The effect of different oxygen pressures on formation of the NiO layer by pulsed laser deposition shows that higher pressure increases the charge carrier density of the film and lowers the dark current in the device. The addition of a monolayer of small molecules containing conjugated pi systems and carboxyl groups at the device interface was also investigated and with correct alignment of the energy levels improves the device performance with respect to the quantum efficiency, responsivity, and photogeneration. The thickness of the Organic layer was also optimized for the device, giving a responsivity of 1.54 X 10(-2) A W-1 in 460 nm light.
Keywords: nickel oxide; organic; oxygen vacancies; photodetector; pulsed laser deposition; surface modifier

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.

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.

Reactivity and catalytic activity of hydrogen atom chemisorbed silver clusters - Manzoor, Dar; Pal, Sourav (Journal of Physical Chemistry A, 2015)
Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different,catalytic applications and low Cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption. On the reactivity and catalytic properties of inert silver clusters Our results affirm that the hydrogen atom chemisorption leads to enhancement the binding energy of the adsorbed O-2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH Silver clusters. Pertinent to the increase in the O-O bond length, a. significant red shift in the O-O Stretching frequency is. also noted in the case,of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and heat Of formation of the final products for the,environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Reactivity and operational stability of N-Tailed TAMLs through kinetic studies of the catalyzed oxidation of orange II by H2O2: synthesis and x-ray structure of an N-Phenyl TAML - Warner, Genoa R.; Mills, Matthew R.; Enslin, Clarissa; Pattanayak, Shantanu; Panda, Chakadola; Panda, Tamas Kumar; Sen Gupta, Sayam; Ryabov, Alexander D.; Collins, Terrence J. (Chemistry A-European Journal, 2015)
{The catalytic activity of the N-tailed (biuret) TAML (tetraamido macrocyclic ligand) activators [Fe{4-XC6H3-1,2-(NCOCMe2NCO)(2)NR}Cl](2-) (3; N atoms in boldface are coordinated to the central iron atom; the same nomenclature is used in for compounds 1 and 2 below), [X
Keywords: Hydrogen peroxide; iron; kinetics; Oxidation; reaction mechanisms

Recent advances in the N-heterocyclic carbene (NHC)-organocatalyzed stetter reaction and related chemistry - Yetra, Santhivardhana Reddy; Patra, Atanu; Biju, Akkattu T. (Synthesis‐Stuttgart, 2015)
Recent developments in the N-heterocyclic carbene (NHC)-catalyzed umpolung of aldehydes followed by their interception with activated carbon–carbon double bonds, namely the Stetter reaction, are presented. Advances in the inter- and intramolecular versions of this reaction, enantioselective transformations as well as the use of unactivated olefins in this type of reaction are discussed.

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

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)

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

RNA stem-loop to G-quadruplex equilibrium controls mature MicroRNA production inside the cell - Pandey, Satyaprakash; Agarwala, Prachi; Jayaraj, Gopal Gunanathan; Gargallo, Raimundo; Maiti, Souvik (Biochemistry, 2015)
The biological role of the existence of overlapping structures in RNA is possible yet remains very unexplored. G-Rich tracts of RNA form G-quadruplexes, while GC-rich sequences prefer stem-loop structures. The equilibrium between alternate structures within RNA may occur and influence its functionality. We tested the equilibrium between G-quadruplex and stem-loop structure in RNA and its effect on biological processes using pre-miRNA as a model system. Dicer enzyme recognizes canonical stem-loop structures in pre-miRNA to produce mature miRNAs. Deviation from stem-loop leads to deregulated mature miRNA levels, providing readout of the existence of an alternate structure per se G-quadruplex-mediated structural interference in miRNA maturation. In vitro analysis using beacon and Dicer cleavage assays indicated that mature miRNA levels depend on relative amounts of K+: and Mg2+ ions, suggesting an ion-dependent structural shift. Further in cellulo studies with and without TmPyP4 (RNA G-quadruplex destabilizer) demonstrated that miRNA biogenesis is modulated by G-quadruplex to stem-loop equilibrium in a subset of pre-miRNAs. Our combined analysis thus provides evidence of the formation of noncanonical G-quaciruplexes in competition with canonical stem-loop structure inside the cell and its effect on miRNA maturation in a comprehensive manner.

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 interfacial tension of solvating diluents and hydrophilic-hydrophobic cross-linkers in hyper-cross-linked solid supports - Mane, Sachin; Ponrathnam, Surendra; Chavan, Nayaku (Industrial & Engineering Chemistry Research, 2015)
The properties of a hyper-cross-linked solid support are the outcome Of the interfacial tension created by solvating/nonsolvating diluents, the hydrophilicity/hydrophobicity of the cross-linkers, and their concentrations. Interestingly, a More hydrophobic diluent and cross-linker as well as a higher concentration of cross-linker-containing copolymer revealed an increase In surface area. A high surface area and low cross-link density (CLD) polymer illustrated higher epoxy content. Importantly, maximum surface area (533 m(2)/g) Was obtained at high CLD; inversely, epoxy,content (1.83 mmol/g) was higher at low CLD polymer. Notably, greater rigidity of cross-linker and its higher concentration increased T-max and T-g; contrarily, greater flexibility of cross-linker and its concentration attenuated T-max and T-g. Thermal study demonstrated the thermostability (300 degrees C) and polymer safe temperature (220 degrees C). Indeed, a lower solubility parameter difference between polymer and swelling solvent produces a higher polymer-solvent interaction parameter, resulting in increased polymer swelling. Polymers with high surface area and low CLD demonstrated greater swelling behavior.

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 the molecular structure of carboxylate-alumoxanes in the enhanced nucleation of polypropylene - Mani, Mohan Raj; Chellaswamy, Ramesh; Marathe, Yogesh N.; Pillai, Vijayamohanan K. (Chemical Communications, 2015)
We have reported the use of carboxylate-alumoxanes as efficient nucleating agents for isotactic polypropylene (iPP) with a possible structural correlation to the nucleation efficiency. The unique, butterfly-like structure of carboxylate-alumoxanes correlates well with the nucleation characteristics of iPP and, for the first time, the impact of a thermally induced, crystalline transition of carboxylate-alumoxanes, which alters neither the structural conformation nor the nucleation efficiency of the transformed material, is demonstrated.

Ruthenium(II)-catalyzed C3 arylation of 2-aroylbenzofurans with arylboronic acids/aryltrifluoroborates via carbonyl-directed C-H bond activation - Paymode, Dinesh J.; Ramana, Chepuri V. (Journal of Organic Chemistry, 2015)
The Ru(II)-catalyzed carbonyl-directed C-H activation with (hetero)arylboron reagents has been executed for the synthesis of 2-aroyl-3-(hetero)arylbenzofurans. A hypothesis founded upon the involvement Of an active carbonatoruthenium(II) complex for a coordinative insertion and the aerobic oxidation of the in situ generated Ru(0) to Ru(II), to continue the catalytic cycle, has been extended.

RXR-carbamate - a novel molecular transporter for skin - Natarajan, Poornemaa; Patil, Kiran M.; Vij, Manika; Yadav, Amit K.; Kumar, Vaijayanti A.; Ganguli, Munia; Fernandes, Moneesha (Molecular Therapy, 2015)
18th Annual Meeting of the American-Society-of-Gene-and-Cell-Therapy (ASGCT), New Orleans, LA, MAY 13-16, 2015

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

Self-assembled vertically aligned gold nanorod super-lattices for ultra-high sensitive detection of molecules - Apte, Amey; Bhaskar, Prashant; Das, Raja; Chaturvedi, Smita; Poddar, Pankaj; Kulkarni, Sulabha (Nano Research, 2015)
We show that self-assembled vertically aligned gold nanorod (VA-GNRs) superlattices can serve as probes or substrates for ultra-high sensitive detection of various molecules. D-glucose and 2,4,6-trinitrotoluene (TNT) have been chosen as model systems due to their very low Raman cross-sections (5.6 x 10(-30) cm(2).molecule(-1).sr(-1) for D-glucose and 4.9 x 10(-31) cm(2). molecule(-1).sr(-1) for TNT) to show that the VA-GNR superlattice assembly offers as low as yoctomole sensitivity. Our experiment on mixed samples of bovine serum albumin (BSA) and D-glucose solutions demonstrate sensitivity for the latter, and the possible extension to real samples. Self-assembled superlattices of VA-GNRs were achieved on a silicon wafer by depositing a drop of solvent containing the GNRs and subsequent solvent evaporation in ambient conditions. An additional advantage of the VA-GNR monolayers is their extremely high reproducible morphology accompanied by ultrahigh sensitivity which will be useful in many fields where a very small amount of analyte is available. Moreover the assembly can be reused a number of times after removing the already present molecules. The method of obtaining VA-GNRs is simple, inexpensive and reproducible. With the help of simulations of monolayers and multilayers it has been shown that superlattices can achieve better sensitivity than monolayer assembly of VA-GNRs.
Keywords: Nanostructures; Raman spectroscopy; self-assemblies; sensors; superlattices

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

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.

Single-layer graphene-assembled 3D porous carbon composites with PVA and Fe3O4 nano-fillers: an interface-mediated superior dielectric and EMI shielding performance - Rao, B. V. Bhaskara; Yadav, Prasad; Aepuru, Radhamanohar; Panda, H. S.; Ogale, Satishchandra; Kale, S. N. (Physical Chemistry Chemical Physics, 2015)
In this study, a novel composite of Fe3O4 nanofiller-decorated single-layer graphene-assembled porous carbon (SLGAPC) with polyvinyl alcohol (PVA) having flexibility and a density of 0.75 g cm(-3) is explored for its dielectric and electromagnetic interference (EMI) response properties. The composite is prepared by the solution casting method and its constituents are optimized as 15 wt% SLGAPC and 20 wt% Fe3O4 through a novel solvent relaxation nuclear magnetic resonance experiment. The PVA-SLGAPC-Fe3O4 composite shows high dielectric permittivity in the range of 1 Hz-10 MHz, enhanced by a factor of 4 as compared to that of the PVA-SLGAPC composite, with a reduced loss by a factor of 2. The temperature dependent dielectric properties reveal the activation energy behaviour with reference to the glass transition temperature (80 degrees C) of PVA. The dielectric hysteresis with the temperature cycle reveals a remnant polarization. The enhanced dielectric properties are suggested to be the result of improvement in the localized polarization of the integrated interface system (Maxwell-Wagner-Sillars (MWS) polarization) formed by the uniform adsorption of Fe3O4 on the surface of SLGAPC conjugated with PVA. The EMI shielding property of the composite with a low thickness of 0.3 mm in the X-band (8.2-12.4 GHz) shows a very impressive shielding efficiency of similar to 15 dB and a specific shielding effectiveness of 20 dB (g cm(-3))(-1), indicating the promising character of this material for flexible EMI shielding applications.

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.

Solid state organic amine detection in a photochromic porous metal organic framework - Mallick, Arijit; Garai, Bikash; Addicoat, Matthew A.; Petkov, Petko St.; Heine, Thomas; Banerjee, Rahul (Chemical Science, 2015)
A new Mg(II) based photochromic porous metal-organic framework (MOF) has been synthesized bearing naphthalenediimide (NDI) chromophoric unit. This MOF (Mg-NDI) shows instant and reversible solvatochromic behavior in presence of solvents with different polarity. Mg-NDI also exhibits fast and reversible photochromism via radical formation. Due to the presence of electron deficient NDI moiety, this MOF exhibits selective organic amine (electron rich) sensing in solid state. The organic amine detection has been confirmed by photoluminescence quenching experiment and visual color change.

Solvent free one-pot multi-component synthesis of beta-azaarene substituted ketones via a Sn-catalyzed C(sp(3))-H functionalization of 2-alkylazaarenes - Chavan, Santosh S.; Pathan, Mohsinkhan Y.; Mulla, Shafeek A. R. (RSC Advances, 2015)
A tin-catalyzed solvent free one-pot multi-component cascade reaction strategy for the direct Michael addition/C(sp(3))-H functionalization of 2-alkylazaarenes with aldehydes and ketones via an aldol reaction has been developed. This is the first report and provides cost effective new access to potent biologically/medicinally important azaarene derivatives with high atom economy.

Solvent-free carbonylation of glycerol with urea using metal loaded MCM-41 catalysts - Kondawar, S. E.; Potdar, A. S.; Rode, C. V. (RSC Advances, 2015)
Reacting glycerol with urea is the most attractive option for the production of glycerol carbonate (GC) as it utilizes two inexpensive chemicals readily available in the chemical cycle. The overall result is the chemical fixation of carbon dioxide. A Zn/MCM-41(im) catalyst prepared by a wet impregnation method exhibited excellent activity for the reaction of glycerol and urea with 75% glycerol conversion and 98% selectivity to GC. Such excellent activity of the catalyst is explained based on the presence of both basic and acidic sites on the same catalyst which activates the glycerol and urea molecules, respectively.

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.

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.

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

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>
International Conference of Computational Methods in Sciences and Engineering (ICCMSE), Kos, GREECE, OCT 03-08, 2010
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.

Supramolecular scaffolds on glass slides as sugar based rewritable sensors for bacteria - Gade, Madhuri; Paul, Ajay; Alex, Catherine; Choudhury, Devika; Thulasiram, Hirekodathakallu V.; Kikkeri, Raghavendra (Chemical Communications, 2015)
We describe here the sugar functionalized beta-cyclodextrin-ferrocene glass slides as fully reversible bacterial biosensors under the influence of external adamantane carboxylic acid. The prototype D-mannose - E. coli ORN 178 and L-fucose - P. aeruginosa interactions serve as a model to illustrate the new approach.

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 characterization of thermotropic liquid crystalline polyimides - Mane, Sachin; Rajan, C. R.; Ponrathnam, Surendra; Chavan, Nayaku (Bulletin of Materials Science, 2015)
Non-symmetrical and linear dyad-based mesogens were synthesised containing imine or ester bridging group. In the present work, due to the absence of branching in diamine-based mesogen, the structure has-rigidity inversely imine/ester bridging groups between two benzene rings imparts-flexible property to the mesogen and consequently rigid-flexible property has been balanced. The synthesised mesogens were characterized by different techniques including nuclear magnetic resonance and Fourier transform infrared spectroscopy. Liquid crystalline polymers (LCPs) were synthesised using pyromellitic dianhydride and 4-[(4-aminobenzylidene)amino]aniline or 4-aminophenyl-4-aminobenzoate. Subsequently, thermotropic liquid crystalline polymers (TLCPs) have also been evaluated to obtain optical microscopy textures at different temperatures which demonstrated interesting and notable changes. It is worth noting that marble-like textures were observed upto 200A degrees C.
Keywords: Diamine; liquid crystalline polymer; mesogen; optical microscopy textures; pyromellitic dianhydride

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, antioxidant, anti-inflammatory, and antimicrobial screening of newer thiophene-fused arylpyrazolyl 1,3,4-oxadiazoles - Mahajan, Pravin S.; Nikam, Mukesh; Chate, Asha; Nimbalkar, Urja; Patil, Vrushali; Bobade, Anil; Chaudhari, Abhay; Deolankar, Dattatray; Javale, Balasaheb; Gill, Charansingh H. (Phosphorus Sulfur and Silicon and the Related Elements, 2015)
A series of newer 1,3,4-oxadiazole derivatives 3a-h, 5a-h containing a thiophene fused with pyrazole moiety of pharmacological significance have been synthesized. The compounds were characterized by H-1 NMR, IR, and mass spectral techniques. The compounds were screened for their in vitro antioxidant, anti-inflammatory and antimicrobial activities. Among them, Compounds 3b (EC50-14.98) and 3f (EC50-12.21) showed significant antioxidant activity. Compound 3a (EC50-15.23) showed good anti-inflammatory activity. Compound 3d was found as the most active derivative against bacterial and fungal strains.
Keywords: 1; 3; 4-Oxadiazole; Anti-inflammatory; Antimicrobial; Antioxidant; EC50; Thiophene-fused pyrazole

Synthesis of 3-ethyl-4-metyl-1h,5-dihydro-2h-pyrrol-2-one by novel palladium(ii)-catalyzed cyclization and ring-closing metathesis - Chavan, Subhash P.; Pathak, Ashok B.; Pawar, Kailash P. (Synthesis-Stuttgart, 2015)
Synthesis of 3-ethyl-4-methyl-1,5-dihydro-2H-pyrrol-2-one is described starting from commercially available allylamine and 4-methoxybenzylamine employing palladium-catalyzed cyclization or ring-closing metathesis as the key steps.
Keywords: antidiabetic; cyclization; glimepiride; lactams; metabolite; pyrrolinone; Ring-closing metathesis

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 silica-polyimide nanocomposite films using aromatic-amino modified silica nanoparticles: mechanical, thermal and morphological investigations - Ghorpade, Ravindra V.; Rajan, C. R.; Chavan, Nayaku; Ponrathnam, S. (Express Polymer Letters, 2015)
Silica nanoparticles were modified with aromatic amino groups and modified-silica/polyimide composite films were prepared using them. 3,3!, 4,4!-Benzophenone tetracarboxylic dianhydride (BTDA) and 4,4!-oxydianiline (ODA) were used as precursors for polyimide matrix. The structures of the modified nanoparticles and hybrid nanocomposites were identified using Fourier Transform Infrared (FTIR) spectrometry. The hybrid composite films were evaluated for mechanical, thermal and morphological characteristics. Morphological results describe a uniform dispersion of silica particles in the polymer matrix. The thermal stability and mechanical properties of polyimide composite were improved, and the decomposition temperature was increased when the amount of silica nanoparticles was increased.
Keywords: hybrid polyimide composites; mechanical properties; Nanocomposites; nanoparticle modification; Thermal properties

Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities - Karne, Anagha S.; Vaval, Nayana; Pal, Sourav; Vasquez-Perez, Jose M.; Koester, Andreas M.; Calaminici, Patrizia (Chemical Physics Letters, 2015)
A comparative study of dipole moments, polarizabilities and hyperpolarizabilities of 16 different molecules is performed employing two completely different theoretical approaches namely, density functional theory (DFT) and coupled cluster singles and doubles (CCSD). Both methods include electron correlation. The CCSD method is more accurate but highly expensive. DFT with auxiliary density allows non-iterative solutions which is computational advantage and useful for large molecules. Dipole moments and polarizability calculations from DFT are in very good agreement with CCSD calculations. However, negative hyperpolarizability values from DFT differ significantly from their CCSD counterparts, whereas positive hyperpolarizabilities show reasonable agreement between these methodologies. (C) 2015 Elsevier B.V. All rights reserved.

Systematic comparison of DFT and CCSD dipole moments, polarizabilities and hyperpolarizabilities (vol 635, pg 168, 2015) - Karne, Anagha S.; Vaval, Nayana; Pal, Sourav; Vasquez-Perez, Jose M.; Koester, Andreas M.; Calaminici, Patrizia (Chemical Physics Letters, 2015)

Tale of RNA G-quadruplex - Agarwala, Prachi; Pandey, Satyaprakash; Maiti, Souvik (Organic & Biomolecular Chemistry, 2015)
G-quadruplexes are non-canonical secondary structures found in guanine rich regions of DNA and RNA. Reports have indicated the wide occurrence of RNA G-quadruplexes across the transcriptome in various regions of mRNAs and non-coding RNAs. RNA G-quadruplexes have been implicated in playing an important role in translational regulation, mRNA processing events and maintenance of chromosomal end integrity. In this review, we summarize the structural and functional aspects of RNA G-quadruplexes with emphasis on recent progress to understand the protein/trans factors binding these motifs. With the revelation of the importance of these secondary structures as regulatory modules in biology, we have also evaluated the various advancements towards targeting these structures and the challenges associated with them. Apart from this, numerous potential applications of this secondary motif have also been discussed.

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 and magnetic field-assisted switching of magnetization and observation of exchange bias in YbCrO3 nanocrystals - Gupta, Preeti; Poddar, Pankaj (Inorganic Chemistry, 2015)
In this paper, we demonstrate an interesting feature in YbCrO3 (YCO) nanocrystals, in which the material shows temperature and external magnetic field-assisted switching (a complete sign reversal) of zero field cooled magnetization (M-ZFC) and observation of exchange bias (EB) as a result of competing spin interaction at low temperature. This feature can be applied in nonvolatile memories, where, simply by changing the magnitude of the H-ext and T, the polarity of the magnetization can be switched between negative and positive. We also observed negative magnetization in YCO. Our results showed that, below its Neel temperature (T-N approximate to 119 K), the M-ZFC crosses over to negative sign for H < 1000 Oe. At 60 K, YCO showed a significant negative M-ZFC approximate to -0.05 emu/g (at 100 Oe) due to the competing effects of Yb3+, Cr3+ spins, thermal activation energy, and Hext. At further lower temperatures, the M-ZFC showed a crossover to positive values, and the crossover temperature showed the dependence on H-ext (similar to 19 K for 100 Oe curve). The YCO also showed H-ext T-dependent H-EB, which changed its sign with T. The observed T-dependent sign reversal in the EB was closely associated with the sign reversal of M-ZFC. The symmetric shift in field-cooled isothermal hysteresis curves confirmed that the observed EB was not due to the unsaturated minor loop. The training cycle further confirmed that the H-EB value decreased to similar to 2% of the initial value of observed EB, which was very small compared to the observed H-EB in YCO, which indicated stable spin configuration at the locally formed ferromagnetic/antiferromagnetic interface.

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

Terahertz spectroscopy and solid-state density functional theory calculations of cyanobenzaldehyde isomers - Dash, Jyotirmayee; Ray, Shaurnik; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin B.; Gonnade, Rajesh G.; Ambade, Ashootosh V.; Joshi, Kavita; Pesala, Bala (Journal of Physical Chemistry A, 2015)
Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

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.

Total synthesis of (R)-lipoic acid and (S)-lipoic acid via an Mn (III)-salen-catalyzed oxidative kinetic resolution - Purude, Abhijeet N.; Pawar, Kailash P.; Patil, Niteen B.; Kalkote, Uttam R.; Chavan, Subhash P. (Tetrahedron-Asymmetry, 2015)
The asymmetric synthesis of both the antipodes of alpha-lipoic acid is described. The total synthesis of racemic and asymmetric lipoic acid is achieved from propane 1,3-diol. This work reports the use of Mn (III)-salen-catalyzed oxidative kinetic resolution as the key step to obtain enantiomerically pure (R)- and (S)-lipoic acid. The undesired product formed during the resolution can be recycled to achieve the desired isomer. (C) 2015 Elsevier Ltd. All rights reserved.

Trifunctional mesoporous silica-based, highly active catalyst for one-pot, three-step cascade reactions - Biradar, Ankush V.; Patil, Vijayshinha S.; Chandra, Prakash; Doke, Dhananjay S.; Asefa, Tewodros (Chemical Communications, 2015)
We report the synthesis of a trifunctional catalyst containing amine, sulphonic acid and Pd nanoparticle catalytic groups anchored on the pore walls of SBA-15. The catalyst efficiently catalyzes one-pot three-step cascade reactions comprising deacetylation, Henry reaction and hydrogenation, giving up to similar to 100% conversion and 92% selectivity to the final product.

Tris-hydroxymethylaminomethane (THAM): a novel organocatalyst for a environmentally benign synthesis of medicinally important tetrahydrobenzo[b]pyrans and pyran-annulated heterocycles - Pandit, Kapil S.; Chavan, Pramod V.; Desai, Uday V.; Kulkarni, Makarand A.; Wadgaonkar, Prakash P. (New Journal of Chemistry, 2015)
simple, efficient and environmentally benign protocol has been developed for the one-pot, multicomponent synthesis of medicinally important tetrahydrobenzo[b]pyrans and pyran-annulated heterocycles using a commercially available, inexpensive, non-toxic, and biodegradable tris-hydroxymethylaminomethane (THAM) as a novel organocatalyst. Ambient reaction conditions, wide scope, avoidance of conventional isolation as well as purification techniques and the reusability of the catalyst for five consecutive runs have improved the practical utility of this multicomponent reaction protocol manifold.

Triterpenoid profiling and functional characterization of the initial genes involved in isoprenoid biosynthesis in neem (Azadirachta indica) - Pandreka, Avinash; Dandekar, Devdutta S.; Haldar, Saikat; Uttara, Vairagkar; Vijayshree, Shinde G.; Mulani, Fayaj A.; Aarthy, Thiagarayaselvam; Thulasiram, Hirekodathakallu V. (BMC Plant Biology, 2015)
Background: Neem tree (Azadirachta indica) is one of the richest sources of skeletally diverse triterpenoids and they are well-known for their broad-spectrum pharmacological and insecticidal properties. However, the abundance of Neem triterpenoids varies among the tissues. Here, we delineate quantitative profiling of fifteen major triterpenoids across various tissues including developmental stages of kernel and pericarp, flower, leaf, stem and bark using UPLC-ESI (+)-HRMS based profiling. Transcriptome analysis was used to identify the initial genes involved in isoprenoid biosynthesis. Based on transcriptome analysis, two short-chain prenyltransferases and squalene synthase (AiSQS) were cloned and functionally characterized. Results: Quantitative profiling revealed differential abundance of both total and individual triterpenoid content across various tissues. RNA from tissues with high triterpenoid content (fruit, flower and leaf) were pooled to generate 79.08 million paired-end reads using Illumina GA.. platform. 41,140 transcripts were generated by d e novo assembly. Transcriptome annotation led to the identification of the putative genes involved in isoprenoid biosynthesis. Two short-chain prenyltransferases, geranyl diphosphate synthase (AiGDS) and farnesyl diphosphate synthase (AiFDS) and squalene synthase (AiSQS) were cloned and functionally characterized using transcriptome data. RT-PCR studies indicated five-fold and ten-fold higher relative expression level of AiSQS in fruits as compared to leaves and flowers, respectively. Conclusions: Triterpenoid profiling indicated that there is tissue specific variation in their abundance. The mature seed kernel and initial stages of pericarp were found to contain the highest amount of limonoids. Furthermore, a wide diversity of triterpenoids, especially C-seco triterpenoids were observed in kernel as compared to the other tissues. Pericarp, flower and leaf contained mainly ring-intact triterpenoids. The initial genes such as AiGDS, AiFDS and AiSQS involved in the isoprenoids biosynthesis have been functionally characterized. The expression levels of AiFDS and AiSQS were found to be in correlation with the total triterpenoid content in individual tissues.
Keywords: Azadirachta indica; Quantitative profiling; Transcriptome; Triterpenoids

Tunable band gap and coercivity of bismuth ferrite-polyaniline core-shell nanoparticles: the role of shell thickness - Chaturvedi, Smita; Das, Raja; Poddar, Pankaj; Kulkarni, Sulabha (RSC Advances, 2015)
We report a tunable band gap of bismuth ferrite-polyaniline core-shell nanoparticles from 2.24 to 1.98 eV and the variation of coercivity from 118 to 100 Oe, by varying the thickness of the polyaniline shell. Bismuth ferrite nanoparticles were synthesized via a chemical route and coating of polyaniline was achieved by a double surfactant layer technique. Coating of polyaniline introduced oxygen vacancies, local distortions and microstrains in the bismuth ferrite lattice which resulted in a change in the Fe-O-Fe bond angle of the bismuth ferrite lattice. This is confirmed with structural analysis tools i.e. X-ray Diffraction, Fourier Transform Infrared Spectroscopy and Raman spectroscopy. Moreover, the absorption of light around 600 nm is increased and photoluminescence emission around 430 nm is decreased, as the thickness of shell is increased, which also indicates the changes in optical properties due to variation in shell thickness. Thus tunability of the band gap and coercivity is achieved as a function of shell thickness in bismuth ferrite-polyaniline core-shell nanoparticles.

Ultra-thin V2O5 nanosheet based humidity sensor, photodetector and its enhanced field emission properties - Pawar, Mahendra S.; Bankar, Prashant K.; More, Mahendra A.; Late, Dattatray J. (RSC Advances, 2015)
We report the synthesis of V2O5 nanosheets by a simple hydrothermal method. The as synthesized V2O5 nanosheets were characterized by Raman spectroscopy, Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and UV-Vis spectroscopy. The humidity sensing behaviors were investigated in the range of 11-97% relative humidity (RH) at room temperature. The maximum sensitivity of 45.3%, response time of similar to 4 min and recovery time of similar to 5 min were observed for the V2O5 nanosheet based sensor. We also demonstrated the V2O5 nanosheets as an ultra-violet photodetector with a sensing response time of similar to 65 s and recovery time of similar to 75 s with a maximum photoresponsivity of similar to 6.2%. Further, we have also carried out field emission (FE) investigations of V2O5 nanosheets under a planar ``Diode'' assembly in an ultrahigh vacuum (UHV) chamber at a base pressure of similar to 1 x 10(-8) mbar. The turn on fields required to draw field emission current densities of 1 mu A cm(-2) and 10 mu A cm(-2) are found to be 1.15 V mu m(-1) and 1.72 V mu m(-1), respectively. We achieved a maximum field emission current density of 1.532 mA cm(-2) at an applied electric field of 3.2 V mu m(-1). The field enhancement factors calculated from the slope of the Fowler-Nordheim (F-N) plot are found to be 8530 and 3530 at low field and high field regions, respectively. Our results open up several avenues towards the successful utilization of V2O5 nanosheets and other metal oxide nanosheets for various nanoelectronics device applications including sensors, photodetector and flat panel displays.

Unprecedented ferrocene-quinoline conjugates: facile proton conduction via 1D helical water chains and a selective chemosensor for Zn(II) ions in water - Ponniah, Joseph S.; Barik, Subrat Kumar; Borthakur, Rosmita; Thakur, Arunabha; Garai, Bikash; Janaa, Sourita; Ghosh, Sundargopal (RSC Advances, 2015)
Two novel ferrocene-quinoline derivatives 3 (C22H19O2N3Fe) and 4 (C34H28O4N6Fe) have been synthesized and structurally characterized. Compound 3 exhibits good proton conductivity through 1D helical water chains. In addition, both compounds 3 and 4 selectively detect Zn2+ ions in water with a detection limit of 2 ppb through multiple channels.

Using Raman and dielectric spectroscopy to elucidate the spin phonon and magnetoelectric coupling in DyCrO3 nanoplatelets - Gupta, Preeti; Poddar, Pankaj (RSC Advances, 2015)
In this study, we report the phonon-mode assignment of DyCrO3 nanoplatelets by Raman spectroscopy. The temperature dependent Raman studies indicate the shift in the phonon frequency of most intense modes of DyCrO3 and the observed change in Raman line-width is correlated with the spin-phonon coupling. The impedance spectroscopy reveals anomalies in the dielectric constant vs. temperature curve in the proximity of the magnetic transitions, thereby hinting towards possible weak magnetoelectric coupling in DyCrO3 nanoplatelets. For the first time, UV-vis absorption spectroscopy and photocatalytic activity of DyCrO3 nanoplatelets have been reported. The optical absorption spectrum gives the band gap similar to 2.8 eV for DyCrO3 nanoplatelets suggesting them as a good candidate for studying photocatalytic activity. The DyCrO3 nanoplatelets showed an efficient photocatalytic activity by degrading 65% methyl orange after 8 h irradiation.

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.

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.

Visible light-triggered disruption of micelles of an amphiphilic block copolymer with BODIPY at the junction - Patil, Naganath G.; Basutkar, Nitin B.; Ambade, Ashootosh V. (Chemical Communications, 2015)
A visible light-cleavable polymer is synthesised to overcome the limitations of UV-sensitive polymers. Photocleavable BODIPY functionalized with an ATRP initiator and alkyne was used to obtain an amphiphilic block copolymer by conducting the click reaction and polymerization simultaneously. Micellar assembly of the polymer was disintegrated under visible light irradiation with controlled release of cargo.

3D interconnected porous graphene sheets loaded with cobalt oxide nanoparticles for lithium-ion battery anodes - Puthusseri, Dhanya; Aravindan, Vanchiappan; Madhavi, Srinivasan; Ogale, Satishchandra (Energy Technology, 2016)
Nanomaterials with high surface-to-volume ratio and tunable electronic and optical properties have expanded their use in variety of applications, especially energy conversion and storage. Here we report on the synthesis of a cobalt oxide (Co3O4)/3D-interconnected porous graphene (PG) nanocomposite by using a simple solvothermal route and its application as a Li-ion battery anode. Among the different compositions investigated, the composite PG-600 (with 50% PG) showed a discharge capacity of 700mAhg(-1) at a current density of 500mAg(-1) and maintained 90% retention after 80cycles. The high surface area of the 3DPG sheets helps the Co3O4 nanoparticles to form a uniform dispersion on the surfaces. The increased surface area (accessibility) and electrical conductivity of the composite result in significant enhancement in the capacity, cycling stability, and rate capability than the native Co3O4 phase.
Keywords: Cobalt oxide; Energy storage; graphene; lithium-ion batteries; Nanocomposites

4 `-Epi-DNA: A DNA Mimic Containing 4 `-hydroxymethyl-alpha-l-Xylo-thymidine with compact backbone like RNA - Bagmare, Seema; Puranik, Vedavati G.; Fernandes, Moneesha; Kumar, Vaijayanti A. (Nucleosides Nucleotides & Nucleic Acids, 2016)
Synthesis of C4-epi-DNA containing 3 5 linkages is reported for the first time. Crystal structure study of the monomer indicated that though the dihedral angle O3-C3-C4-C5 in this case would be like in RNA, the sugar conformation would remain like that in DNA. The study of the effect of this backbone configuration in DNA with respect to its binding to cDNA and RNA is reported in this note.
Keywords: 4 `-hydroxymethyl nucleosides C4 `-epi-DNA; Antisense Oligonucleotide

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.

Adsorption of strontium (II) metal ions using phosphonate-functionalized polymer - Bhosle, S. M.; Ponrathnam, S.; Tambe, S. S.; Chavan, N. N. (Bulletin of Materials Science, 2016)
Diethyl[3-(methoxydimethylsilyl)propyl]phosphonate (DMPP) polymer was synthesized for the strontium (II) metal ion recovery using diethylallylphosphonate as staring material. Diethylallylphosphonate was reacted with poly(methylhydro)siloxane (MW 1900-2000 g mol (-1) ) in the presence of Speier's catalyst. The synthesized monomer was characterized by IR, (1) H NMR, (1 3) C NMR and FT-IR spectroscopy techniques, and the synthesized polymers were characterized by IR and NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and solubility. The synthesized polymer was used for sequestering strontium metal from the aqueous solution. The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbent dose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, and pseudo-first- and second-order models. Results of this study indicate that the synthesized polymer DMPP has been effective in removing Sr(II) from the aqueous solution.

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

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

Antioxidative metabolites synthesized by marine pigmented vibrio sp and its protection on oxidative deterioration of membrane lipids - Pawar, Ravindra; Mohandass, Chellandi; Dastager, Syed Gulam; Kolekar, Yogesh M.; Malwankar, Rahul (Applied Biochemistry and Biotechnology, 2016)
Bacterial strain Vibrio sp. (PIGB 184) isolated from water samples of the Arabian Sea and identified through 16S rRNA demonstrated the production of pigmentary antioxidants with higher ABTS activities 90.9 +/- 0.42 % in comparison with the standard commercial pigmented antioxidant, quercetin 88.8 +/- 1.4 %. Antioxidative metabolites of this strain substantially inhibit the lipid peroxidation (LPO) reactions tested in sheep liver and brain. The antioxidant compounds produced by the Vibrio sp. (PIGB 184), analysed by GC-MS, reveals that it is composed mostly of phenol, 2,4-bis(1,1-dimethylethyl) and pyrrolo[1,2-a]pyrazine-1,4-dione,hexahydro-3-(2-methylpropyl). The interrelationship assessed between LPO and the phenolic compounds showed significant correlation with anti-LPO properties (R (2) = 0.9698 to 0.9861). These compounds are responsible for obstruction of harmful radical associated biochemical reactions in biological systems. Pigmented metabolites also tested for attributive biological properties against pathogenic bacteria showed prominent inhibition towards Gram-positive organisms (31.25 to 62.5 mu g ml(-1)). From this study, it may be suggested that the marine bacterium PIGB 184 could be used as a potential bio-resource for antioxidants and needs to be worked out for mass production.
Keywords: Antioxidants; Lipid peroxidation; Marine pigmented bacteria; Pathogen inhibition; Phenolics

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 total synthesis of L-allo-1-deoxynojirimycin - Chavan, Subhash P.; Dumare, Nilesh B.; Pawar, Kailash P.; Chavan, Prakash N.; Khairnar, Lalit B. (Arkivoc, 2016)
Asymmetric total synthesis of L-allo-1-deoxynojirimycin (L-allo-DNJ) was achieved from cis-butene-1,4-diol by employing Sharpless asymmetric dihydroxylation, stereoselective flash dihydroxylation and ring enlargement reactions as key steps.
Keywords: diastereoselective flash dihydroxylation; ring-enlargement reaction; sharpless asymmetric dihydroxylation

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)

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.

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

Bioavailability studies of curcumin-sophorolipid nano-conjugates in the aqueous phase: role in the synthesis of uniform gold nanoparticles - Darne, Priti A.; Mehta, Mihir R.; Agawane, Sachin B.; Prabhune, Asmita (RSC Advances, 2016)
The major limiting factors for curcumin to be accepted as a modern drug, despite its widespread applications, are its low aqueous solubility, low retention time and poor bioavailability. When subjected to a mild physical stress, curcumin is observed to internalize within the micellar hydrophobic core of oleic acid sophorolipid resulting in the formation of curcumin-sophorolipid nanoconjugates (CurSL). These bio-composites show enhanced retention time and increased bioavailability of curcumin in rat models. In the presence of gold salts, CurSL act as potent reducing and capping agents, resulting in the synthesis of monodispersed, spherical gold nanoparticles (CurSL-GNPs) of 8-10 nm in size. Physicochemical, morphological and optical characteristics of both the nanoparticles are discussed based on spectroscopic absorption, photoluminescence (PL), dynamic light scattering (DLS), zeta potential, SEM and TEM measurements. FTIR spectroscopy signatures of these nanoparticles confirm the retention of functional groups in the end products. A retention time of 2 hours in blood plasma and an increase in curcumin recovery by about 150 times that previously reported were observed in the pharmacokinetic (pK(a)) studies performed on Wistar rats. The bio-distribution of gold nanoparticles in rats was studied using EDX, which revealed their presence in different vital organs. The absence of unusual legions or necrosis in histopathological analysis of vital organs in all the rat models suggests the use of curcuminsophorolipid nano-conjugates enhances curcumin bioavailability and the Cur-SL based nano-gold formulation is a good drug delivery carrier.

Biological activity of sophorolipids and their possible use as antiviral agents - Borsanyiova, Maria; Patil, Amrita; Mukherji, Ruchira; Prabhune, Asmita; Bopegamage, Shubhada (Folia Microbiologica, 2016)
Sophorolipids are surface active glycolipids consisting of a hydrophilic sophorose unit and a hydrophobic portion composed of a fatty acid tail. Crude sophorolipid sample contains both acidic and lactonic forms of sophorolipid with different degrees of acetylation and varying lengths of the fatty acid chains depending on the substrates used in the production process. Carboxylic end in the acidic form of the fatty acid is free, whereas in the lactonic form, it is internally esterified. Sophorolipids show different physicochemical properties with wide range of applications for each structural compound. Lactonic form of sophorolipids shows surface tension reducing ability and biological activity, whereas the acidic form possesses better foam forming ability and higher solubility. Presence of acetyl groups gives hydrophilic nature to the sophorolipids which promotes its antiviral and cytokine-stimulating properties. The aim of this review is to explore and suggest the plausibility of sophorolipids as therapeutic and prophylactic agents for the treatment of viral diseases.

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.

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.

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.

Bronsted-acid-mediated divergent reactions of betti bases with indoles: an approach to chromeno[2,3-b]indoles through intramolecular dehydrogenative C2-alkoxylation of indole - Deb, Mohit L.; Pegu, Choitanya Dev; Deka, Bhaskar; Dutta, Prantu; Kotmale, Amol S.; Baruah, Pranjal K. (European Journal of Organic Chemistry, 2016)
Divergent reactions of various 1-(aminoalkyl) naphthols and 2-(aminoalkyl) phenols (commonly known as Betti bases) with indoles under Bronsted acid catalysis is reported. With the reaction strategies, one can efficiently synthesize important indole derivatives such as 3-(alpha,alpha-diarylmethyl)indoles and chromeno[2,3-b]indoles. Furthermore, we disclose here a new C-C bond-cleavage reaction, in which naphthol and phenol behave as leaving groups to produce diarylmethanes. Inexpensive reagents such as p-toluenesulfonic acid monohydrate and molecular iodine are used to catalyze the reactions. No metal catalyst is required. The starting material of the reactions, Betti bases, are easily prepared from a three-component reaction of naphthol/phenol, aldehydes, and secondary amines. The mechanisms for the reactions are established through some control experiments. Quinone methide is the key intermediate for all the reactions reported herein.
Keywords: Betti bases; C-O bond formation; Dearylation; Fused-ring systems; nitrogen heterocycles

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.

Cetyl alcohol and oleic acid sophorolipids exhibit anticancer activity - Dubey, P.; Raina, P.; Prabhune, A.; Kaul-Ghanekar, R. (International Journal of Pharmacy and Pharmaceutical Sciences, 2016)
Objective: Sophorolipids (SLs) are glycolipid biosurfactants that have been shown to have anticancer activity. We investigated the anti-cancer activity of cetyl alcohol sophorolipids (CAS) and oleic acid sophorolipids (OAS) in breast cancer (MCF-7, MDA-MB-231), cervical cancer (SiHa, HeLa) and non-cancerous (HaCaT and RAW264.7) cell lines. Methods: For cell viability assay, MCF-7, MDA-MB-231, SiHa, HeLa, HaCaT and RAW264.7 cell lines were treated with different concentrations (0-160 μg/ml) of OAS and CAS for 24h. The cell viability was determined by MTT dye uptake method. Cell proliferation assay was determined by using trypan blue dye exclusion method. Results: Our preliminary data shows that compared to OAS, CAS exhibited more significant reduction in the viability of MCF-7, MDA-MB-231 and SiHa. However, compared to CAS, OAS induced more decrease in viability in HeLa cells. Interestingly, both the types of SLs did not affect the viability of non-cancerous cells. Moreover, CAS, when used as a coating material, induced proliferation in macrophage cell line, RAW264.7. Conclusion: The present study provides an important clue towards the anti-cancer potential of OAS and CAS derived from Candida bombicola. Interestingly, the ability of CAS to promote the proliferation of non-cancerous cells suggests its future application as a scaffold for enhancing the adhesion and proliferation of normal cells.

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

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 fruit and vegetable peels as bioadsorbents - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Current Science, 2016)
Fruit and vegetable peel (FVP) wastes are a commonly generated organic waste from both households and food-processing industries. However, FVPs are low-cost lignocellulosic materials that have some potential for reutilization. For its particular reutilization, the characterization of FVP is essential. In this regard, the present study provides a detailed physico-chemical characterization of commonly used FVPs such as pomegranate, pineapple, watermelon, garlic, green pea and pigeon pea. The materials were characterized by SEM, FTIR and TGA/DTG. Various properties of these materials, such as porosity, particle density, bulk density, surface charges, point of zero charge, surface pH, water absorption capacity and BET surface area were determined. The BET surface area of FVP was found in the range 1.0-1.4 m(2)/g. Water absorption capacity was highest for watermelon peel (11.5 ml/g), while it was lowest for pigeon pea peel (5.5 ml/g). Point of zero charge and surface pH of all FVPs were in the acidic range 3-6. The surface of FVP was irregular and rough with some pores. Thermal analysis showed that FVPs are thermally stable below 150 degrees C. The results of this study provide an understanding of the properties of FVPs and suggest that the materials can be used as a low-cost adsorbent.
Keywords: Bioadsorbent; fruit and vegetable peels; organic waste; physico-chemical characterization

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.

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.

Chord length distribution to particle size distribution - Pandit, Ajinkya V.; Ranade, Vivek V. (AICHE Journal, 2016)
A simple model is presented to extract the particle size distribution (PSD) from the chord length distribution measured using a focused beam reflectance measurement probe. The model can be implemented using simple spread sheeting tools and does not require the description of additional parameters as opposed to previous models. The model was validated for two systems consisting of spherical ceramic beads by comparing model predicted PSD against the PSD obtained through image analysis (IA). Then, the model was evaluated by considering various systems consisting of irregularly shaped particles (sand/zinc dust/plasma alumina). Model predictions accurately predicted the mean but over-predicted the variance of the PSD in comparison with the PSD obtained from IA. However, overall, a reasonable agreement was observed. Finally, the model was shown to be accurate in predicting PSD in comparison with the measured PSD for systems of practical relevance such as for paracetamol and p-aminophenol crystals. (c) 2016 American Institute of Chemical Engineers AIChE J, 62: 4215-4228, 2016

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.

Complete metagenome sequencing based bacterial diversity and functional insights from basaltic hot spring of Unkeshwar, Maharashtra, India - Mehetre, Gajanan T.; Paranjpe, Aditi S.; Dastager, Syed Gulam; Dharne, Mahesh S. (Genomics Data, 2016)
Unkeshwar hot springs are located at geographical South East Deccan Continental basalt of India. Here, we report the microbial community analysis of this hot spring using whole metagenome shotgun sequencing approach. The analysis revealed a total of 848,096 reads with 212.87Mbps with 50.87% G+C content. Metagenomic sequences were deposited in SRA database with accession number (SUB1242219). Community analysis revealed 99.98% sequences belonging to bacteria and 0.01% to archaea and 0.01% to Viruses. The data obtained revealed 41 phyla including bacteria and Archaea and including 719 different species. In taxonomic analysis, the dominant phyla were found as, Actinobacteria (56%), Verrucomicrobia (24%), Bacteriodes (13%), Deinococcus-Thermus (3%) and firmicutes (2%) and Viruses (2%). Furthermore, functional annotation using pathway information revealed dynamic potential of hot spring community in terms of metabolism, environmental information processing, cellular processes and other important aspects. Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis of each contig sequence by assigning KEGG Orthology (KO) numbers revealed contig sequences that were assigned to metabolism, organismal system, Environmental Information Processing, cellular processes and human diseases with some unclassified sequences. The Unkeshwar hot springs offer rich phylogenetic diversity and metabolic potential for biotechnological applications.

Conformational dynamics of GPCR dimers is dependent on membrane cholesterol - Sengupta, Durba; Prasanna, Xavier; Chattopadhyay, Amitabha (Biophysical Journal, 2016)
60th Annual Meeting of the Biophysical-Society, Los Angeles, CA, FEB 27-MAR 02, 2016

Contriving a catalytically active structure from an inert conformation: a density functionalinvestigation of Al, Hf, and Ge doping of Au-20 tetrahedral clusters - Manzoor, Dar; Krishnamurty, Sailaja; Pal, Sourav (Journal of Physical Chemistry C, 2016)
The transformation of an inert structure into a catalytically active conformation has immense potential from a structural engineering point of view. In the present work, we explored methods of achieving such a transformation through a density-functional-based study. Au-20 is known be one of the most stable and catalytically inert gold clusters, with a well-known tetrahedral structure. We demonstrate the transformation of the inert Au-20 conformation into a highly active catalytic cluster through selective doping with Hf and Ge atoms. Depending on the dopant, the inert tetrahedral Au-20 cluster evolves into either an endohedral or a hollow-cage-like conformation. The structural changes are manifested in the catalytic properties as well, with the result that the transformed doped cages exhibit extremely low activation barriers for the environmentally important CO oxidation reaction as compared to reported inert Au-20 cluster. The activation barriers for CO oxidation are particularly low (<0.12 eV) when germanium is directly involved in the CO oxidation. Thus, the current work highlights the importance of engineering structural properties of metal nanoclusters with the help of heteroatom dopants for future applications in efficient catalysis.

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.

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

Convenient synthesis of alpha,alpha `- homo- and alpha,alpha `-hetero-bifunctionalized poly(epsilon-caprolactone)s by ring opening polymerization: the potentially valuable precursors for miktoarm star copolymers - Patil, Sachin S.; Tawade, Bhausaheb V.; Wadgaonkar, Prakash P. (Journal of Polymer Science Part A-Polymer Chemistry, 2016)
Two new ring opening polymerization (ROP) initiators, namely, (3-allyl-2-(allyloxy)phenyl)methanol and (3-allyl-2-(prop-2-yn-1-yloxy)phenyl)methanol each containing two reactive functionalities viz. allyl, allyloxy and allyl, propargyloxy, respectively, were synthesized from 3-allylsalicyaldehyde as a starting material. Well defined -allyl, -allyloxy and -allyl, -propargyloxy bifunctionalized poly(epsilon-caprolactone)s with molecular weights in the range 4200-9500 and 3600-10,900 g/mol and molecular weight distributions in the range 1.16-1.18 and 1.15-1.16, respectively, were synthesized by ROP of epsilon-caprolactone employing these initiators. The presence of -allyl, -allyloxy and -allyl, -propargyloxy functionalities on poly(epsilon-caprolactone)s was confirmed by FT-IR, H-1, C-13 NMR spectroscopy, and MALDI-TOF analysis. The kinetic study of ROP of epsilon-caprolactone with both the initiators revealed the pseudo first order kinetics with respect to epsilon-caprolactone consumption and controlled behavior of polymerization reactions. The usefulness of -allyl, -allyloxy functionalities on poly(epsilon-caprolactone) was demonstrated by performing the thiol-ene reaction with poly(ethylene glycol) thiol to obtain (mPEG)(2)-PCL miktoarm star copolymer. -Allyl, -propargyloxy functionalities on poly(epsilon-caprolactone) were utilized in orthogonal reactions i.e copper catalyzed alkyne-azide click (CuAAC) with azido functionalized poly(N-isopropylacrylamide) followed by thiol-ene reaction with poly(ethylene glycol) thiol to synthesize PCL-PNIPAAm-mPEG miktoarm star terpolymer. The preliminary characterization of A(2)B and ABC miktoarm star copolymers was carried out by H-1 NMR spectroscopy and gel permeation chromatography (GPC). (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 844-860
Keywords: 3-allylsalicyaldehyde; alpha `-allyloxy and alpha-allyl; alpha `-propargyloxy bifunctionalized poly (epsilon-caprolactone)s; alpha-allyl; atom transfer radical polymerization; orthogonal reactions; ring-opening polymerization; star copolymers

Crosslinked polymer embedded Cu/Ag for comparative drug adsorption and kinetics evaluation - Mane, Sachin; Ponrathnam, Surendra; Chavan, Nayaku (International Journal of Polymeric Materials and Polymeric Biomaterials, 2016)
Two-dimensional crosslinked polymer (2-DCP) was synthesized for evaluation of drug adsorption and kinetics thereof. Further, polymer properties were evaluated and parameters such as contact time and adsorption isotherm were also studied. Herein, contact time demonstrated 83% and 85% of drug loading in an acidic medium for two-dimensional crosslinked polymer embedded copper and silver (2-DCP-Cu/Ag), respectively in 24h. Initial 4h is the exponential drug loading period whereas drug loading was increased gradually after 4h. Salbutamol loading was well-fitted to Langmuir adsorption isotherm, which indicated a monolayer drug adsorption with respect to 2-DCP-Cu/Ag. Pseudo first- and pseudo second-order kinetics was evaluated to perceive the drug adsorption mechanism and equilibrium adsorption capacity. Monolayer drug adsorption with chemisorption mechanism was observed for 2-DCP-Cu/Ag. In addition to this, decomposition temperature of polymer was 440 and 325 degrees C while glass transition temperature of polymer was 280 and 200 degrees C before and after metal modification, respectively. (A=aqueous phase; B=organic phase; C=drug solution; D=drug loaded polymer; E=enlarged drug loaded polymer.) [GRAPHICS] .
Keywords: Adsorption isotherm; adsorption kinetics; crosslink polymer; drug loading; langmuir adsorption isotherm; salbutamol

Crystal structure, computational studies, and stereoselectivity in the synthesis of 2-aryl-thiazolidine-4-carboxylic acids via insitu imine intermediate - Jagtap, Rohidas M.; Rizvi, Masood A.; Dangat, Yuvraj B.; Pardeshi, Satish K. (Journal of Sulfur Chemistry, 2016)
This article presents the synthesis of (2R/2S,4R)-2-aryl-thiazolidine-4-carboxylic acids via nucleophilic addition of L-Cysteine on aromatic aldehydes involving a yield and time-effective room temperature reaction in an aqueous DMSO medium in the presence of NaHCO3 as a base. The synthesized diastereomers were spectroscopically characterized and quantified for diastereomeric excess by liquid chromatography-mass spectrometry analysis. The impact of the type and position of substituent in aromatic aldehydes on reaction time, % yield, H-1 NMR shift at newly formed chiral center [C(2)-H], and diastereomeric excess (de%) have been investigated. A plausible mechanism for stereoselectivity via an in situ imine intermediate is proposed using real-time IR monitoring of the synthetic reaction based on the significant signals at 1597, 1593cm(-1) for imine (C=N) stretching. The imine mechanism for stereoselectivity was further supported by NMR studies of azomethine C-13 NMR signals at 159, 160ppm and by the single crystal structure of hitherto unknown (2S,4R)-3-(tert-butoxycarbonyl)-2-(2-hydroxyphenyl)thiazolidine-4-carbox ylic acid (3a) obtained as a major diastereomer in the synthesis of the butyloxy carbonyl (BOC) derivative of (2R/2S,4R)-2-(2-hydroxyphenyl)thiazolidine-4-carboxylic acid. The significant ortho-OH effect of phenolic hydroxyl group leading to strong hydrogen bondings plays a vital role in the formation of 2S,4R BOC derivative stereoselectively. The frontier molecular orbitals, possible electronic excitations, IR band characterizations, and reactivity parameters of newly reported compound (3a) have been predicted using quantum chemical descriptors from density functional theory. The theoretical exploration of experimental spectra using time-dependent DFT indicated a (-*) transition between HOMO and LUMO in the ultraviolet region.
Keywords: 2-aryl-thiazolidine-4-carboxylic acids; density function theory; frontier molecular orbitals; imine intermediate; X-ray crystal structure

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

Diethylamine-catalyzed environmentally benign synthesis of 1-oxo-hexahydroxanthenes and bis-coumarins at ambient temperature - Kupwade, Ravindra V.; Pandit, Kapil S.; Desai, Uday V.; Kulkarni, Makarand A.; Wadgaonkar, Prakash P. (Research on Chemical Intermediates, 2016)
An extremely simple, economical and environmentally benign protocol has been described for one-pot synthesis of 1-oxo-hexahydroxanthenes by pseudo three-component condensation between salicylaldehydes and dimedone, cyclohexane-1,3dione or 5-methyl cyclohexane-1,3-dione using diethylamine as the catalyst. Based upon the mechanism of the reaction, the protocol has been extended towards the synthesis of tetraketones and bis-coumarins.

Differentiating process performance of various coagulants in removal of congo red and orange G dyes - Prajapati, Kavita; Sorokhaibam, Laxmi Gayatri; Bhandari, Vinay M.; Killedar, D. J.; Ranade, Vivek V. (International Journal of Chemical Reactor Engineering, 2016)
Two refractory azo dyes-Congo red and Orange G, especially at high concentrations were subjected to coagulation with different conventional coagulants and newer formulations developed from Aluminum sulfate, Iron (III) chloride, Aluminium chloride, Poly diallydimethylammonium chloride (Poly DADMAC) and Poly Aluminium Chloride (PAC). The highest COD reduction of 99 % was obtained with PAC SAB 18 (Powder Grade PAC) for Congo red at pH 4.5 while the color removal of 99 % was achieved with almost all the coagulants in the present study at specific pH within 3-8. The optimum dose for the iron-based coagulant is 200 mg/L while that of aluminum-based coagulants and PAC is 150-200 mg/L. Results showed that Orange G was more difficult to remove with a maximum COD removal of 65 % and 35 % color removal using various formulations. The combinational formulations of inorganic-inorganic and inorganic- organic produced a substantial enhancement in COD and color removal and reduced sludge. PAC-Fe30/70 produces the minimum sludge of 50 mL/g on Congo red. pH in the range 3-9 showed high reductions in COD and color (90-99 %) for Congo red while jerky rise in COD and color reduction was observed in the case of Orange G after pH 9. An attempt to understand the dye coagulation mechanism has been made based on the specific difference in dye structure and cation speciation.
Keywords: coagulation; Congo red; dye removal; Orange G; Wastewater treatment

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

Dynamic, reversible oxidative addition of highly polar bonds to a transition metal - Bertermann, Ruediger; Boehnke, Julian; Braunschweig, Holger; Dewhurst, Rian D.; Kupfer, Thomas; Muessig, Jonas H.; Pentecost, Leanne; Radacki, Krzysztof; Sen, Sakya S.; Vargas, Alfredo (Journal of the American Chemical Society, 2016)
The combination of Pt complexes and indium trihalides leads to compounds that form equilibria in solution between their In X oxidative addition (OA) products (Pt indyl complexes) and their metal-only Lewis pair (MOLP) isomers (LnPt -> InX3). The position of the equilibria can be altered reversibly by changing the solvent, while the equilibria can be reversibly and irreversibly driven toward the MOLP products by addition of further donor ligands. The results mark the first observation of an equilibrium between MOLP and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. In addition, we present the first structural characterization of MOLP and oxidative addition isomers of the same compound. The relative energies of the MOLP and OA isomers were calculated by DFT methods, and the possibility of solvent-mediated isomerization is discussed.

Effect of mixed acid catalysis on pretreatment and enzymatic digestibility of sugar cane bagasse - Pal, Siddhartha; Joy, Shereena; Kumbhar, Pramod; Trimukhe, K. D.; Varma, Anjanikumar; Padmanabhan, Sasisanker (Energy & Fuels, 2016)
Aqueous pretreatment using homogeneous acid catalyst is considered as a low-cost technology in the production of lignocellulosic bioethanol. To establish the synergism of mixed acids, pilot-level aqueous pretreatments of bagasse covering a wide range of combined severity (CS) were carried out. To investigate the effect of application of mixture of acids on xylose hydrolysis as well as glucose hydrolysis via pretreatment and enzymatic hydrolysis, the following three combinations of acids were explored: (1) oxalic acid + sulfuric acid (organic + mineral acid), (2) phosphoric + sulfuric acid (mineral acids), and (3) ferric chloride + sulfuric acid (Lewis acid with a mineral acid). Of the pretreatments evaluated, the synergism was most pronounced for the combination of sulfuric and phosphoric acid, which resulted in more than 90% conversion of hemicellulose to xylose and 70% conversion of cellulose to glucose through enzymatic hydrolysis. Fourier transform infrared (FTIR) studies of pretreated samples showed higher syringyl/guaiacyl (S/G) ratio for sulfuric and phosphoric acid combination pretreatment, leading to higher enzymatic conversion. FTIR and dynamic light scattering (DLS) experiments conducted on pretreated sugar cane bagasse provided useful correlation with regard to the pretreatment type, particle size, and enzymatic hydrolysis.

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

Effect of process intensifying parameters on the hydrodynamic cavitation based degradation of commercial pesticide (methomyl) in the aqueous solution - Raut-Jadhav, Sunita; Saini, Daulat; Sonawane, Shirish; Pandit, Aniruddha (Ultrasonics Sonochemistry, 2016)
Methomyl, a carbamate pesticide, is classified as a pesticide of category-1 toxicity and hence shows harmful effects on both human and aquatic life. In the present work, the degradation of methomyl has been studied by using hydrodynamic cavitation reactor (HC) and its combination with intensifying agents such as H2O2, fenton reagent and ozone (hybrid processes). Initially, the optimization of operating parameters such pH and inlet pressure to the cavitating device (circular venturi) has been carried out for maximizing the efficacy of hydrodynamic cavitation. Further degradation study of methomyl by the application of hybrid processes was carried out at an optimal pH of 2.5 and the optimal inlet pressure of 5 bar. Significant synergetic effect has been observed in case of all the hybrid processes studied. Synergetic coefficient of 5.8, 13.41 and 47.6 has been obtained by combining hydrodynamic cavitation with H2O2, fenton process and ozone respectively. Efficacy of individual and hybrid processes has also been obtained in terms of energy efficiency and extent of mineralization. HC + Ozone process has proved to be the most effective process having highest synergetic coefficient, energy efficiency and the extent of mineralization. The study has also encompassed the identification of intermediate by-products generated during the degradation and has proposed the probable degradation pathway. It has been conclusively established that hydrodynamic cavitation in the presence of intensifying agents can effectively be used for complete degradation of methomyl. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: Advanced Oxidation Processes (AOPs); Hydrodynamic cavitation; Methomyl; Synergetic coefficient; Venturi

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

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

Effects of thermal treatment of ZnO-ZnCr2O4 catalyst on the particle size and product selectivity in dehydrocyclization of crude glycerol and ethylenediamine - Sarkari, Reema; Krishna, Vankudoth; Sudhakar, Medak; Rao, Tumula Venkateshwar; Padmasri, Aytam Hari; Srinivas, Darbha; Venugopal, Akula (Kinetics and Catalysis, 2016)
The ZnO-ZnCr2O4 (Zn-Cr-O) sample obtained by decomposition of Zn-Cr hydrotalcite precursor was subjected to the thermal treatment at different temperatures and the physico-chemical properties of the Zn-Cr-O system were compared with its catalytic behavior in dehydrocyclization of crude glycerol and ethylenediamine (EDA). Upon high temperature treatment of Zn-Cr-O the Cr6+ ions underwent autoreduction to form stable Cr3+ species and the particle size of both ZnO and ZnCr2O4 increased dramatically. Thermal effect did not influence the intermolecular cyclisation of EDA to form pyrazine. By contrast, an inversely proportional dependence was found between the rate of formation of 2-methylpyrazine and the particle size of Zn-Cr-O whereas the rate of 2-pyrazinylmethanol was directly proportional to the particle size.

Efficient access to alkynylated quinalizinones via the gold(I)-catalyzed aminoalkynylation of alkynes - Shinde, Popat S.; Shaikh, Aslam C.; Patil, Nitin T. (Chemical Communications, 2016)
The gold-catalyzed aminoalkynylation of alkynes for the synthesis of quinalizinones is reported. For instance, the reaction of pyridinoalkynes with 1-[(triisopropylsilyl)-ethynyl]-1,2-benziodoxol-3(1H)-one (TIPS-EBX) in the presence of a catalytic amount of AuCl at 50 8C afforded alkynylated quinalizinones in 57-87% yields.

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

Efficient strategy for the construction of both enantiomers of the octahydropyrroloquinolinone ring system: total synthesis of (+)-aspidospermidine - Pandey, Ganesh; Burugu, Shiva Kumar; Singh, Pushpendra (Organic Letters, 2016)
An efficient and highly stereoselective intramolecular [3 + 2] cycloaddition of nonstabilized azomethine ylide generated from a designed bicyclic aminal precursor is reported for the synthesis of both (-)- and (+)-octahy-dropyrroloquinolinone. One of the enantiomers is further advanced to accomplish the total synthesis of (+)-aspidospermidine.

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

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

Electron detachment and subsequent structural changes of water clusters - Das, Susanta; Sengupta, Turbasu; Dutta, Achintya Kumar; Pal, Sourav (Journal of Physical Chemistry A, 2016)
A cost-effective equation of motion coupled cluster method, EOMIP-CCSD(2), is used to investigate vertical and adiabatic ionization potential as well as ionization-induced structural changes of water clusters and compared with CCSD(T), CASPT2, and MP2 methods. The moderate N-5 scaling and low storage requirement yields EOMIP-CCSD (2) calculation feasible even for reasonably large molecules and clusters with accuracy comparable to CCSD(T) method at much cheaper computational cost. Our calculations shed light on the authenticity of EOMIP-CCSD(2) results and establish a reliable method to study of ionization energy of molecular clusters. We have further investigated the performance of several classes of DFT functionals for ionization energies of water clusters to benchmark the results and to get a reliable functionals for the same.

Endohedrally doped gold nanocages: efficient catalysts for O-2 activation and CO oxidation - Manzoor, Dar; Krishnamurty, Sailaja; Pal, Sourav (Physical Chemistry Chemical Physics, 2016)
Gold nanocages are the most attractive catalytic materials as all the atoms in the cage type clusters reside on the surface, making them available for chemisorption by reacting molecules. Due to a hollow space at the center, their chemical and catalytic properties can be tuned effectively and easily by endohedral doping. While a significant experimental and theoretical understanding is currently available on the structural and electronic properties of doped gold cages, very little information is available on their reactivity and catalytic behavior. In the present work, with the help of density functional theory calculations we demonstrate that endohedral doping leads to a notable increase in the binding energy of molecular oxygen on the gold nanocages. The enhancement in the O-2 binding energy on the doped gold cages is also confirmed by a significant decrease in the Au-O and an increase in the O-O bond lengths, corroborated by a red shift (similar to 250 cm(-1)) in the O-O stretching frequency as compared to the pristine cage. Furthermore, interestingly, the doped gold cages show very low activation barriers for the environmentally important CO oxidation reaction as compared to the pristine gold cage. Importantly, the decrease in the barrier height is comparatively greater for the rate limiting step of O-O-C-O intermediate formation and as a result the CO oxidation is expected to be more facile on the doped gold cages. Thus, the current study highlights the role of heteroatom doping in imparting new chemical and catalytic properties to gold cages and is expected to spur further research in the design of efficient gold nanocatalysts.

Enhanced field emission behavior of layered MoSe2 - Suryawanshi, Sachin R.; Pawbake, Amit S.; Pawar, Mahendra S.; Jadkar, Sandesh R.; More, Mahendra A.; Late, Dattatray J. (Materials Research Express, 2016)
Herein, we report one step facile chemical vapor deposition method for synthesis of single-layer MoSe2 nanosheets with average lateral dimension similar to 60 mu m on 300 nm SiO2/Si and n-type silicon substrates and field emission investigation of MoSe2/Si at the base pressure of similar to 1 x 10(-8) mbar. The morphological and structural analyses of the as-deposited single-layer MoSe2 nanosheets were carried out using an optical microscopy, Raman spectroscopy and atomic force microscopy. Furthermore, the values of turn-on and threshold fields required to extract an emission current densities of 1 and 10 mu A cm(-2), are found to be similar to 1.9 and similar to 2.3 V mu m(-1), respectively. Interestingly, the MoSe2 nanosheet emitter delivers maximum field emission current density of similar to 1.5 mA cm(-2) at a relatively lower applied electric field of similar to 3.9 V mu m(-1). The long term operational current stability recorded at the preset values of 35 mu A over 3 hr duration and is found to be very good. The observed results demonstrates that the layered MoSe2 nanosheet based field emitter can open up many opportunities for their potential application as an electron source in flat panel display, transmission electron microscope, and x-ray generation. Thus, the facile one step synthesis approach and robust nature of single-layer MoSe2 nanosheets emitter can provide prospects for the future development of practical electron sources.
Keywords: atomically thin nanosheets; chemical vapor deposition; field emission; layered MoSe2

Enhanced nucleation of polypropylene by metal-organic frameworks (MOFs) based on aluminium dicarboxylates: influence of structural features - Mani, Mohan Raj; Chellaswamy, Ramesh; Marathe, Yogesh N.; Pillai, Vijayamohanan K. (RSC Advances, 2016)
Metal-organic frameworks (MOFs) based on aluminium dicarboxylates provide a new platform for the enhanced nucleation of isotactic polypropylene (iPP). For instance, aluminium dicarboxylates exhibit a unique butterfly-like structure similar to that of carboxylate-alumoxanes and correlates well with the nucleation characteristics of iPP. A subtle change in the structure of the ligand backbone (fumarate/succinate) does not alter the framework structure despite changing the hydrophilic/hydrophobic character and its subsequent nucleation characteristics. This suggests that the nucleating agent should facilitate favourable interaction with hydrophobic iPP for efficient nucleation. Further, a systematic variation of the alkyl chain length in the Al-dicarboxylate does not change the nucleation efficiency considerably, even though it increases the distance between the octahedral alumina chains in the metal-organic framework, suggesting that the butterfly-like structure present in the framework is a key aspect for nucleation. Finally, the significance of the orientational conformation of the dicarboxylate around the metal centre for the nucleation is confirmed by the poor nucleation efficiency of chromium and zirconium suberate MOFs where the orientation of suberate would be different from that of aluminium suberate due to the difference in the ligation of the carboxylate group. The present work thus provides valuable pathways for developing new nucleating agents based on MOFs with appropriate selection and orientation of the organic linkers around the metal centre.

Evaluating the anticancer activity and nanoparticulate nature of homeopathic preparations of Terminalia chebula - Wani, Kirtee; Shah, Nilesh; Prabhune, Asmita; Jadhav, Arun; Ranjekar, Prabhakar; Kaul-Ghanekar, Ruchika (Homeopathy, 2016)
Background: Breast cancer is the most common cancer diagnosed among women and is the second leading cause of cancer death. Homeopathic medicines are part of the alternative medicines that are given as a supportive therapy in breast cancer. The objective of this study was to investigate the anticancer activity of commercially available homeopathic preparations of Terminalia chebula (TC) and evaluate their nanoparticulate nature. Methods: Mother tincture (MT) and other homeopathic preparations (3X, 6C and 30C) of TC were tested for their effect on the viability of breast cancer (MDAMB231 and MCF7) and non-cancerous (HEK 293) cell lines by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Cell growth assay was performed to analyze the effect of the different potencies on the growth kinetics of breast cancer cells. MT and 6C were evaluated for the presence of nanoparticles by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results: MT decreased the viability of breast cancer (MDAMB231 and MCF7) and non-cancerous (HEK 293) cells. However, the other potencies (3X, 6C and 30C) decreased the viability of only breast cancer cells without affecting the viability of the non-cancerous cells. All the potencies, MT, 3X, 6C and 30C, reduced growth kinetics of breast cancer cells, more specifically at 1:10 dilution at 24, 48 and 72 h. Under SEM, MT appeared as a mesh-like structure whereas under TEM, it showed presence of nanoclusters. On the other hand, 6C potency contained 20 nm sized nanoparticles. Conclusion: The current study reports the anticancer activity of homeopathic preparations of TC against breast cancer and reveals their nanoparticulate nature. These preliminary results warrant further mechanistic studies at both in vitro and in vivo levels to evaluate the potential of TC as nanomedicine in breast cancer.

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