Triclabendazole: An Intriguing Case of Co-existence of Conformational and Tautomeric Polymorphism

The crystal polymorphism of the anthelmintic drug, triclabendazole (TCB), is described. Two anhydrates (Forms I and II), three solvates, and an amorphous form have been previously mentioned. This study reports the crystal structures of Forms I (1) and II (2). These structures illustrate the uncommon phenomenon of tautomeric polymorphism. TCB exists as two tautomers A and B. Form I (Z'=2) is composed of two molecules of tautomer A while Form II (Z'=1) contains a 1:1 mixture of A and B. The polymorphs are also characterized by using other solid-state techniques (differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), PXRD, FT-IR, and NMR spectroscopy). Form I is the higher melting form (m.p.: 177 degrees C, Delta Hf=approximate to 105 +/- 4 Jg-1) and is the more stable form at room temperature. Form II is the lower melting polymorph (m.p.: 166 degrees C, Delta Hf=approximate to 86 +/- 3 Jg-1) and shows high kinetic stability on storage in comparison to the amorphous form but it transforms readily into Form I in a solution-mediated process. Crystal structure analysis of co-crystals 3-11 further confirms the existence of tautomeric polymorphism in TCB. In 3 and 11, tautomer A is present whereas in 4-10 the TCB molecule exists wholly as tautomer B. The DFT calculations suggest that the optimized tautomers A and B have nearly the same energies. Single point energy calculations reveal that tautomer A (in Form I) exists in two low-energy conformations, whereas in Form II both tautomers A and B exist in an unfavorable high-energy conformation, stabilized by a five-point dimer synthon. The structural and thermodynamic features of 1-11 are discussed in detail. Triclabendazole is an intriguing case in which tautomeric and conformational variations co-exist in the polymorphs.

Variation of diffusivity with the cation radii in molten salts of superionic conductors containing iodine anion: A molecular dynamics study

A molecular dynamics study of the dependence of diffusivity of the cation on ionic radii in molten AgI is reported. We have employed modified Parinello-Rahman-Vashistha interionic pair potential proposed by Shimojo and Kobayashi.(1) Our results suggest that the diffusivity of the cation exhibits an increase followed by a decrease as the ionic radius is increased. Several structural and dynamical properties are reported.

Selective colorimetric detection of nanomolar Cr (VI) in aqueous solutions using unmodified silver nanoparticles

In this study we present a colorimetric detection method for Cr (VI) in aqueous solution based on as synthesized silver nanoparticles (Ag NPs) without surface functionalization. The method principle involves reduction of Cr (VI) to Cr (III) by excess reductant present in as synthesized Ag NP dispersion, and subsequent aggregation of Ag NPs by Cr (III) leading to red-shift of the surface plasmon resonance (SPR) peak. The UV-vis absorption spectra. Zeta potentials, dynamic light scattering measurements, and scanning electron microscopy (SEM) confirmed the aggregation of the Ag NPs. Under the optimized conditions, a good linear relationship (correlation coefficient r=0.981) was obtained between the ratio of the absorbance at 550 nm to that at 390 nm (A(550/390)) and the concentration of Cr (VI) over the range of 10(-3)-10(-9) M 50 mg/L to 50 ng/L]. The reported probe has a limit of detection down to 1 nM, which, to the best of our knowledge, is the lowest ever reported for the colorimetric detection of Cr (VI). Furthermore, a remarkable feature of this method is that it involves a simple technique exhibiting high selectivity to Cr (VI) over other tested heavy metal ions. (C) 2012 Elsevier BM. All rights reserved.

Synthesis and spectral characterization of cyclotriphosphazene based 18-membered macrocycles

New 18-membered cyclotriphosphazene-containing macrocycles 7-10 were obtained by 1 + 1 condensation reaction of dispiro-N3P3(C12H8O2)(2)((N(Me)N=CH)(2) N4C20H26)] (2) with N,N'-dimethyl-ethylenediamine-1,4-diyldimethylenebis(4-methyl-2-formylph enol) (3), N,N'-dimethyl-ethylenediamine-1,4-diyldimethylenebis(4,5-dimethyl-2-form ylphenol) (4), N,N'-dimethyl-ethylenediamine-1,4-diyldimethylenebis(5-chloro-2-formylph enol) (5) and N,N'-dimethyl-ethylenediamine-1,4-diyldimethylenebis(5-bromo-2-formylphe nol) (6), respectively. (C) 2012 Elsevier B.V. All rights reserved.

Analytical Field-Effect Method for Extraction of Subgap States in Thin-Film Transistors

We present an analytical field-effect method to extract the density of subgap states (subgap DOS) in amorphous semiconductor thin-film transistors (TFTs), using a closed-form relationship between surface potential and gate voltage. By accounting the interface states in the subthreshold characteristics, the subgap DOS is retrieved, leading to a reasonably accurate description of field-effect mobility and its gate voltage dependence. The method proposed here is very useful not only in extracting device performance but also in physically based compact TFT modeling for circuit simulation.

Bismuth catalyzed growth of silicon nanowires by electron beam evaporation

Silicon nanowires (NWs) have been grown in the vapor phase for the first time with bismuth (Bi) as a catalyst using the electron beam evaporation method at a low substrate temperature of 280 degrees C. The grown Si nanowires were randomly oriented on the substrate with an average length of 900 nm for a deposition time of 15 min. Bi faceted nanoparticles (crowned) at the end of the grown Si nanowires have been observed and attributed to the Vapor-Liquid-Solid (VLS) growth mechanism. Transmission Electron Microscopy analysis on the nanowires revealed their single crystalline nature and interestingly bismuth particles were observed in Si nanowires. The obtained results have shown a new window for Si nanowires growth with bismuth as a catalyst. (C) 2012 Elsevier B.V. All rights reserved.

AdFT: An Adaptive Framework for Fault Tolerance on Large Scale Systems using Application Malleability

Exascale systems of the future are predicted to have mean time between failures (MTBF) of less than one hour. Malleable applications, where the number of processors on which the applications execute can be changed during executions, can make use of their malleability to better tolerate high failure rates. We present AdFT, an adaptive fault tolerance framework for long running malleable applications to maximize application performance in the presence of failures. AdFT framework includes cost models for evaluating the benefits of various fault tolerance actions including checkpointing, live-migration and rescheduling, and runtime decisions for dynamically selecting the fault tolerance actions at different points of application execution to maximize performance. Simulations with real and synthetic failure traces show that our approach outperforms existing fault tolerance mechanisms for malleable applications yielding up to 23% improvement in application performance, and is effective even for petascale systems and beyond.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

As(3)p: A Fast Algorithm to Search Structurally Similar Protiens

Protein structure comparison is essential for understanding various aspects of protein structure, function and evolution. It can be used to explore the structural diversity and evolutionary patterns of protein families. In view of the above, a new algorithm is proposed which performs faster protein structure comparison using the peptide backbone torsional angles. It is fast, robust, computationally less expensive and efficient in finding structural similarities between two different protein structures and is also capable of identifying structural repeats within the same protein molecule.

A soluble diacylglycerol acyltransferase is involved in triacylglycerol biosynthesis in the oleaginous yeast Rhodotorula glutinis

The biosynthesis of triacylglycerol (TAG) occurs in the microsomal membranes of eukaryotes. Here, we report the identification and functional characterization of diacylglycerol acyltransferase (DGAT), a member of the 10 S cytosolic TAG biosynthetic complex (TBC) in Rhodotorula glutinis. Both a full-length and an N-terminally truncated cDNA clone of a single gene were isolated from R. glutinis. The DGAT activity of the protein encoded by RgDGAT was confirmed in vivo by the heterologous expression of cDNA in a Saccharomyces cerevisiae quadruple mutant (H1246) that is defective in TAG synthesis. RgDGAT overexpression in yeast was found to be capable of acylating diacylglycerol (DAG) in an acyl-CoA-dependent manner. Quadruple mutant yeast cells exhibit growth defects in the presence of oleic acid, but wild-type yeast cells do not. In an in vivo fatty acid supplementation experiment, RgDGAT expression rescued quadruple mutant growth in an oleate-containing medium. We describe a soluble acyl-CoA-dependent DAG acyltransferase from R. glutinis that belongs to the DGAT3 class of enzymes. The study highlights the importance of an alternative TAG biosynthetic pathway in oleaginous yeasts.

Modeling of agglomeration inside a droplet with nanosuspensions in an acoustic field

This short communication reports results of particle agglomeration details of an acoustically levitated nanosilica droplet. The droplet undergoes thermo-physical and morphological changes under external heating load (convective or radiative) forming different solid structures due to particle agglomeration. We report an agglomeration model based on population balance approach coupled with species and energy conservation equations in the liquid phase and compare it with the experimentally observed structure formations using high speed photography. The analysis is able to predict similar spherical bowl shaped morphologies as observed experimentally using scanning electron microscopy and laser induced fluorescence. (C) 2012 Elsevier Ltd. All rights reserved.

Durability of Pt/C and Pt/MC-PEDOT catalysts under simulated start-stop cycles in polymer electrolyte fuel cells

A composite of mesoporous carbon (MC) with poly(3,4-ethylenedioxythiophene) (PEDOT) is studied as catalyst support for platinum nanoparticles. The durability of commercial Pt/carbon and Pt/MC-PEDOT as cathode catalyst is investigated by invoking air-fuel boundary at the anode side so as to foster carbon corrosion at the cathode side of a polymer electrolyte fuel cell (PEFC). Pt/MC-PEDOT shows higher resistance to carbon corrosion in relation to Pt/C. Electrochemical techniques such as cyclic voltammetry (CV) and impedance measurements are used to evaluate the extent of degradation in the catalyst layer. It is surmised that the resistance of MC-PEDOT as catalyst support toward electrochemical oxidation makes Pt/MC-PEDOT a suitable and stable cathode catalyst for PEFCs.

Throughput analysis of primary and secondary networks in a shared IEEE 802.11 system

In this paper, we analyze the coexistence of a primary and a secondary (cognitive) network when both networks use the IEEE 802.11 based distributed coordination function for medium access control. Specifically, we consider the problem of channel capture by a secondary network that uses spectrum sensing to determine the availability of the channel, and its impact on the primary throughput. We integrate the notion of transmission slots in Bianchi's Markov model with the physical time slots, to derive the transmission probability of the secondary network as a function of its scan duration. This is used to obtain analytical expressions for the throughput achievable by the primary and secondary networks. Our analysis considers both saturated and unsaturated networks. By performing a numerical search, the secondary network parameters are selected to maximize its throughput for a given level of protection of the primary network throughput. The theoretical expressions are validated using extensive simulations carried out in the Network Simulator 2. Our results provide critical insights into the performance and robustness of different schemes for medium access by the secondary network. In particular, we find that the channel captures by the secondary network does not significantly impact the primary throughput, and that simply increasing the secondary contention window size is only marginally inferior to silent-period based methods in terms of its throughput performance.