Ternary ion-pair complexation: a protocol for chiral discrimination and the assignment of absolute configuration of chiral hydroxy acids

The study demonstrates the utility of ternary ion-pair complex formed among BINOL (1,1'-Bi-2-naphthol), a carboxylic acid and an organic base, such as, dimethylpyridine (DMAP), 1,4-diazabicyclo2.2.2]octane (DABCO), as a versatile chiral solvating agent (CSA) for the enantiodiscrimination of carboxylic acids, measurement of enantiomeric excess (ee) and the assignment of absolute configuration of hydroxy acids. The proposed mechanism of ternary complex has wider application for testing the enantiopurity owing to the fact that the binary mixture using BINOL alone does not serve as a solvating agent for their discrimination. In addition, the developed protocol has an excellent utility for the assignment of the absolute configurations of hydroxy acids.

Stereoselective geminal difunctionalization of vinyl arenes mediated by the bromonium ion

An anti-Markovnikov geminal oxyamination of styrenyl alkenes in an intermolecular fashion using the umpolung strategy mediated by the bromonium ion is reported. Isotope labeling studies confirm the migration of the phenyl group in the semipinacol rearrangement.

Negative differential resistance and effect of defects and deformations in MoS2 armchair nanoribbon metal-oxide-semiconductor field effect transistor

In this work, we present a study on the negative differential resistance (NDR) behavior and the impact of various deformations (like ripple, twist, wrap) and defects like vacancies and edge roughness on the electronic properties of short-channel MoS2 armchair nanoribbon MOSFETs. The effect of deformation (3 degrees-7 degrees twist or wrap and 0.3-0.7 angstrom ripple amplitude) and defects on a 10 nm MoS2 ANR FET is evaluated by the density functional tight binding theory and the non-equilibrium Green's function approach. We study the channel density of states, transmission spectra, and the I-D-V-D characteristics of such devices under the varying conditions, with focus on the NDR behavior. Our results show significant change in the NDR peak to valley ratio and the NDR window with such minor intrinsic deformations, especially with the ripple. (C) 2013 AIP Publishing LLC.

Morphology and electrochemical performance of graphene nanosheet array for Li-ion thin film battery

Highly branched and porous graphene nanosheet synthesized over different substrates as anode for Lithium ion thin film battery. These films synthesized by microwave plasma enhanced chemical vapor deposition at temperature 700 degrees C. Scanning electron microscopy and X-ray photo electron spectroscopy are used to characterize the film surface. It is found that the graphene sheets possess a curled and flower like morphology. Electrochemical performances were evaluated in swezelock type cells versus metallic lithium. A reversible capacity of 520 mAh/g, 450 mAh/g and 637 mAh/g was obtained after 50 cycles when current rate at 23 mu A cm(2) for CuGNS, NiGNS and PtGNS electrodes, respectively. Electrochemical properties of thin film anode were measured at different current rate and gave better cycle life and rate capability. These results indicate that the prepared high quality graphene sheets possess excellent electrochemical performances for lithium storage. (C) 2013 Elsevier Ltd. All rights reserved.

Computationally Efficient and Accurate Modeling of Li-ion Battery

A computationally efficient Li-ion battery model has been proposed in this paper. The battery model utilizes the features of both analytical and electrical circuit modeling techniques. The model is simple as it does not involve a look-up table technique and fast as it does not include a polynomial function during computation. The internal voltage of the battery is modeled as a linear function of the state-of-charge of the battery. The internal resistance is experimentally determined and the optimal value of resistance is considered for modeling. Experimental and simulated data are compared to validate the accuracy of the model.

Excellent Performance of Few-Layer Borocarbonitrides as Anode Materials in Lithium-Ion Batteries

Borocarbonitrides (BxCyNz) with a graphene-like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid-state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon-rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100cycles) and rate capability over widely varying current density values (0.05-1Ag(-1)). B0.15C0.73N0.12 has a very high specific capacity of 710mAhg(-1) at 0.05Ag(-1). With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900mAhg(-1) at 0.05Ag(-1). It is believed that the solid-electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz .

Variable field ion traps

This paper presents a technique to vary the electric field within a cylindrical ion trap (CIT) mass spectrometer while it is in operation. In this technique, the electrodes of the CIT are split into number of mini-electrodes and different voltages are applied to these split-electrodes to achieve the desired field. In our study we have investigated two geometries of the split-electrode CIT. In the first, we retain the flat endcap electrodes of the CIT but split the ring electrode into five mini-rings. In the second configuration, we split the ring electrode of the CIT into three mini-rings and also divide the endcaps into two mini-discs. By applying different potentials to the mini-rings and mini-discs of these geometries we have shown that the field within the trap can be optimized to desired values. In our study, two different types of fields were targeted. In the first, potentials were adjusted to obtain a linear electric field and, in the second, a controlled higher order even multipole field was obtained by adjusting the potential. We have shown that the different potentials required can be derived from a single RF generator by connecting appropriate capacitor terminations to split electrodes. The field within the trap can be modified by changing the values of the external capacitors. (C) 2013 Elsevier B.V. All rights reserved.

Controlling Light Absorption in Charge-Separating Core/Shell Semiconductor Nanocrystals

Semiconductor nanocrystals of different formulations have been extensively studied for use in thin-film photovoltaics. Materials used in such devices need to satisfy the stringent requirement of having large absorption cross sections. Hence, type-II semiconductor nanocrystals that are generally considered to be poor light absorbers have largely been ignored. In this article, we show that type-II semiconductor nanocrystals can be tailored to match the light-absorption abilities of other types of nanostructures as well as bulk semiconductors. We synthesize type-II ZnTe/CdS core/shell nanocrystals. This material is found to exhibit a tunable band gap as well as absorption cross sections that are comparable to (die. This result has significant implications for thin-film photovoltaics, where the use of type-II nanocrystals instead of pure semiconductors can improve charge separation while also providing a much needed handle to regulate device composition.

Performance analysis of boron nitride embedded armchair graphene nanoribbon metal-oxide-semiconductor field effect transistor with Stone Wales defects

We study the performance of a hybrid Graphene-Boron Nitride armchair nanoribbon (a-GNR-BN) n-MOSFET at its ballistic transport limit. We consider three geometric configurations 3p, 3p + 1, and 3p + 2 of a-GNR-BN with BN atoms embedded on either side (2, 4, and 6 BN) on the GNR. Material properties like band gap, effective mass, and density of states of these H-passivated structures are evaluated using the Density Functional Theory. Using these material parameters, self-consistent Poisson-Schrodinger simulations are carried out under the Non Equilibrium Green's Function formalism to calculate the ballistic n-MOSFET device characteristics. For a hybrid nanoribbon of width similar to 5 nm, the simulated ON current is found to be in the range of 265 mu A-280 mu A with an ON/OFF ratio 7.1 x 10(6)-7.4 x 10(6) for a V-DD = 0.68 V corresponding to 10 nm technology node. We further study the impact of randomly distributed Stone Wales (SW) defects in these hybrid structures and only 2.5% degradation of ON current is observed for SW defect density of 3.18%. (C) 2014 AIP Publishing LLC.

Topological Excitations in Semiconductor Heterostructures

Topological defects play an important role in the melting phenomena in two-dimensions. In this work, we report experimental observation of topological defect induced melting in two-dimensional electron systems (2DES) in the presence of strong Coulomb interaction and disorder. The phenomenon is characterised by measurement of conductivity which goes to zero in a Berezinskii-Kosterlitz-Thouless like transition. Further evidence is provided via low-frequency conductivity noise measurements.

Green ionothermal synthesis of hierarchical nanostructures of SnS2 and their Li-ion storage properties

Flower-like hierarchical architectures of layered SnS2 have been synthesized ionothermally for the first time, using a water soluble EMIM]BF4 ionic liquid (IL) as the solvent medium. At lower reaction temperatures, the hierarchical structures are formed of few-layered polycrystalline 2D nanosheet-petals composed of randomly oriented nanoparticles of SnS2. The supramolecular networks of the IL serve as templates on which the nanoparticles of SnS2 are glued together by combined effects of hydrogen bonding, electrostatic, hydrophobic and imidazolium stacking interactions of the IL, giving rise to polycrystalline 2D nanosheet-petals. At higher reaction temperatures, single crystalline plate-like nanosheets with well-defined crystallographic facets are obtained due to rapid inter-particle diffusion across the IL. Efficient surface charge screening by the IL favors the aggregation of individual nanosheets to form hierarchical flower-like architectures of SnS2. The mechanistic aspects of the ionothermal bottom-up hierarchical assembly of SnS2 nanosheets are discussed in detail. Li-ion storage properties of the pristine SnS2 samples are examined and the electrochemical performance of the sample synthesized at higher temperatures is found to be comparable to that reported for pristine SnS2 samples in the literature.

Phase and Dimensionality of Tin Oxide at graphene nanosheet array and its Electrochemical performance as anode for Lithium Ion Battery

We incorporated tin oxide nanostructures into the graphene nanosheet matrix and observed that the phase of tin oxide varies with the morphology. The highest discharge capacity and coulumbic efficiency were obtained for SnO phase of nanoplates morphology. Platelet morphology of tin oxide shows more reversible capacity than the nanoparticle (SnO2 phase) tin oxide. The first discharge capacity obtained for SnO@GNS is 1393 and 950 mAh/g for SnO2@GNS electrode at a current density of 23 mu A/cm(2). A stable capacity of about 1022 and 715 mAh/g was achieved at a current rate of 23 mu A/cm(2) after 40 cycles for SnO@GNS and SnO2@GNS anodes, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

Residue specific contributions to stability and activity inferred from saturation mutagenesis and deep sequencing

Multiple methods currently exist for rapid construction and screening of single-site saturation mutagenesis (SSM) libraries in which every codon or nucleotide in a DNA fragment is individually randomized. Nucleotide sequences of each library member before and after screening or selection can be obtained through deep sequencing. The relative enrichment of each mutant at each position provides information on its contribution to protein activity or ligand-binding under the conditions of the screen. Such saturation scans have been applied to diverse proteins to delineate hot-spot residues, stability determinants, and for comprehensive fitness estimates. The data have been used to design proteins with enhanced stability, activity and altered specificity relative to wild-type, to test computational predictions of binding affinity, and for protein model discrimination. Future improvements in deep sequencing read lengths and accuracy should allow comprehensive studies of epistatic effects, of combinational variation at multiple sites, and identification of spatially proximate residues.

Allosteric Transition Induced by Mg2+ Ion in a Transactivator Monitored by SERS

We demonstrate the utility of the surface-enhanced Raman spectroscopy (SERS) to monitor conformational transitions in protein upon ligand binding. The changes in protein's secondary and tertiary structures were monitored using amide and aliphatic/aromatic side chain vibrations. Changes in these bands are suggestive of the stabilization of the secondary and tertiary structure of transcription activator protein C in the presence of Mg2+ ion, whereas the spectral fingerprint remained unaltered in the case of a mutant protein, defective in Mg2+ binding. The importance of the acidic residues in Mg2+ binding, which triggers an overall allosteric transition in the protein, is visualized in the molecular model. The present study thus opens up avenues toward the application of SERS as a potential tool for gaining structural insights into the changes occurring during conformational transitions in proteins.