Transition metal-free Minisci reaction promoted by NCS, and TBHP: acylation of heteroarenes

A method for acylation for heteroarenes under metal-free conditions has been described using NCS as an additive and TBHP as an oxidant. This method has been successfully employed in acylation of a variety of aldehyde with heteroarenes. The application of the method has been illustrated in synthesizing isoquinoline derived natural products. This strategy provides an efficient, mild and inexpensive method for acylation of heteroarenes. (C) 2015 Elsevier Ltd. All rights reserved.

Mechanism to synthesize a `moving optical mark' at solid-ambient interface for the estimation of thermal diffusivity of solid

supporting unsteady heat flow with its ambient-humidity; invokes phase transformation of water-vapour molecule and synthesize a `moving optical-mark' at sample-ambient-interface. Under tailored condition, optical-mark exhibits a characteristic macro-scale translatory motion governed by thermal diffusivity of solid. For various step-temperature inputs via cooling, position-dependent velocities of moving optical-mark are measured at a fixed distance. A new approach is proposed. `Product of velocity of optical-mark and distance' versus `non-dimensional velocity' is plotted. The slope reveals thermal diffusivity of solid at ambient-temperature; preliminary results obtained for Quartz-glass is closely matching with literature. (C) 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes

We report here the first general method for the geminal diamination and an intermolecular metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent. A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labelling studies and the control studies have provided unambiguous evidences for the phenyl migration and hydride migration in the oxidative geminal difunctionalization process mediated by Phl(OCOCF3)(2) and m-CPBA, respectively through a semi-pinacol rearrangement. (C) 2016 Elsevier Ltd. All rights reserved.

Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

A Perspective on Computer Assisted Assessment Techniques for Short Free-Text Answers

Computer Assisted Assessment (CAA) has been existing for several years now. While some forms of CAA do not require sophisticated text understanding (e.g., multiple choice questions), there are also student answers that consist of free text and require analysis of text in the answer. Research towards the latter till date has concentrated on two main sub-tasks: (i) grading of essays, which is done mainly by checking the style, correctness of grammar, and coherence of the essay and (ii) assessment of short free-text answers. In this paper, we present a structured view of relevant research in automated assessment techniques for short free-text answers. We review papers spanning the last 15 years of research with emphasis on recent papers. Our main objectives are two folds. First we present the survey in a structured way by segregating information on dataset, problem formulation, techniques, and evaluation measures. Second we present a discussion on some of the potential future directions in this domain which we hope would be helpful for researchers.

Electrical and Plasmonic Properties of Ligand-Free Sn4+-Doped In2O3 (ITO) Nanocrystals

Sn4+-doped In2O3 (ITO) is a benchmark transparent conducting oxide material. We prepared ligand-free but colloidal ITO (8nm, 10% Sn4+) nanocrystals (NCs) by using a post-synthesis surface-modification reaction. (CH3)(3)OBF4 removes the native oleylamine ligand from NC surfaces to give ligand-free, positively charged NCs that form a colloidal dispersion in polar solvents. Both oleylamine-capped and ligand-free ITO NCs exhibit intense absorption peaks, due to localized surface plasmon resonance (LSPR) at around =1950nm. Compared with oleylamine-capped NCs, the electrical resistivity of ligand-free ITO NCs is lower by an order of magnitude (approximate to 35mcm(-1)). Resistivity over a wide range of temperatures can be consistently described as a composite of metallic ITO grains embedded in an insulating matrix by using a simple equivalent circuit, which provides an insight into the conduction mechanism in these systems.

Structure-rheology relationship in a sheared lamellar fluid

The structure-rheology relationship in the shear alignment of a lamellar fluid is studied using a mesoscale model which provides access to the lamellar configurations and the rheology. Based on the equations and free energy functional, the complete set of dimensionless groups that characterize the system are the Reynolds number (rho gamma L-2/mu), the Schmidt number (mu/rho D), the Ericksen number (mu(gamma)/B), the interface sharpness parameter r, the ratio of the viscosities of the hydrophilic and hydrophobic parts mu(r), and the ratio of the system size and layer spacing (L/lambda). Here, rho and mu are the fluid density and average viscosity, (gamma) over dot is the applied strain rate, D is the coefficient of diffusion, B is the compression modulus, mu(r) is the maximum difference in the viscosity of the hydrophilic and hydrophobic parts divided by the average viscosity, and L is the system size in the cross-stream direction. The lattice Boltzmann method is used to solve the concentration and momentum equations for a two dimensional system of moderate size (L/lambda = 32) and for a low Reynolds number, and the other parameters are systematically varied to examine the qualitative features of the structure and viscosity evolution in different regimes. At low Schmidt numbers where mass diffusion is faster than momentum diffusion, there is fast local formation of randomly aligned domains with ``grain boundaries,'' which are rotated by the shear flow to align along the extensional axis as time increases. This configuration offers a high resistance to flow, and the layers do not align in the flow direction even after 1000 strain units, resulting in a viscosity higher than that for an aligned lamellar phase. At high Schmidt numbers where momentum diffusion is fast, the shear flow disrupts layers before they are fully formed by diffusion, and alignment takes place by the breakage and reformation of layers by shear, resulting in defects (edge dislocations) embedded in a background of nearly aligned layers. At high Ericksen number where the viscous forces are large compared to the restoring forces due to layer compression and bending, shear tends to homogenize the concentration field, and the viscosity decreases significantly. At very high Ericksen number, shear even disrupts the layering of the lamellar phase. At low Ericksen number, shear results in the formation of well aligned layers with edge dislocations. However, these edge dislocations take a long time to anneal; the relatively small misalignment due to the defects results in a large increase in viscosity due to high layer stiffness and due to shear localization, because the layers between defects get pinned and move as a plug with no shear. An increase in the viscosity contrast between the hydrophilic and hydrophobic parts does not alter the structural characteristics during alignment. However, there is a significant increase in the viscosity, due to pinning of the layers between defects, which results in a plug flow between defects and a localization of the shear to a part of the domain.

Structural, Optical, and Piezoelectric Response of Lead-Free Ba0.95Mg0.05Zr0.1Ti0.9O3 Nanocrystalline Powder

Nanocrystalline powders of Ba1-xMgxZr0.1Ti0.9O3 (x = 0.025-0.1) were synthesized via citrate assisted sol-gel method. Interestingly, the one with x = 0.05 in the system Ba1-xMgxZr0.1Ti0.9O3 exhibited fairly good piezoelectric response aside from the other physical properties. The phase and structural confirmation of synthesized powder was established by X-ray powder diffraction (XRD) and Raman Spectroscopic techniques. Two distinct Raman bands i.e., 303 and 723 cm(-1) characteristic of tetragonal phase were observed. Thermogravimetric analysis (TGA) was performed to evaluate the phase decomposition of the as-synthesized Ba0.95Mg0.05Zr0.1Ti0.9O3 sample as a function of temperature. The average crystallite size associated with Ba0.95Mg0.05Zr0.1Ti0.9O3 was calculated using Scherrer formula based on the XRD data and was found to be 25 nm. However, Scanning and Transmission Electron Microscopy studies revealed the average crystallite size to be in the range of 30-40 nm, respectively. Kubelka-Munk function was employed to determine the optical band gap of these nanocrystallites. A piezoelectric response of 26 pm/V was observed for Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystal by Piezoresponse Force Microscopy (PFM) technique. Photoluminescence (PL) study carried out on these nanocrystals exhibited a blue emission (470 nm) at room temperature.

Density functional theory based study of chlorine doped WS2-metal interface

Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS2. (C) 2016 AIP Publishing LLC.

Effect of particle size of sand and surface asperities of reinforcement on their interface shear behaviour

This paper investigates the effect of particle size of sand and the surface asperities of reinforcing material on their interlocking mechanism and its influence on the interfacial shear strength under direct sliding condition. Three sands of different sizes with similar morphological characteristics and four different types of reinforcing materials with different surface features were used in this study. Interface direct shear tests on these materials were performed in a specially developed symmetric loading interface direct shear test setup. Morphological characteristics of sand particles were determined from digital image analysis and the surface roughness of the reinforcing materials was measured using an analytical expression developed for this purpose. Interface direct shear tests at three different normal stresses were carried out by shearing the sand on the reinforcing material fixed to a smooth surface. Test results revealed that the peak interfacial friction and dilation angles are hugely dependent upon the interlocking between the sand particles and the asperities of reinforcing material, which in turn depends on the relative size of sand particles and asperities. Asperity ratio (AS/D-50) of interlocking materials, which is defined as the ratio of asperity spacing of the reinforcing material and the mean particle size of sand was found to govern the interfacial shear strength with highest interfacial strength measured when the asperity ratio was equal to one, which represents the closest fitting of sand particles into the asperities. It was also understood that the surface roughness of the reinforcing material influences the shear strength to an extent, the influence being more pronounced in coarser particles. Shear bands in the interface shear tests were analysed through image segmentation technique and it was observed that the ratio of shear band thickness (t) to the median particle size (D-50) was maximum when the AS/D-50 was equal to one. (C) 2015 Elsevier Ltd. All rights reserved.

Insights into the Structural Dynamics of Nucleocytoplasmic Transport of tRNA by Exportin-t

Exportin-t (Xpot) transports mature 5'- and 3'-end processed tRNA from the nucleus to the cytoplasm by associating with a small G-protein Ran (RAs-related nuclear protein), in the nucleus. The release of tRNA in cytoplasm involves RanGTP hydrolysis. Despite the availability of crystal structures of nuclear and cytosolic forms of Xpot, the molecular details regarding the sequential events leading to tRNA release and subsequent conformational changes occurring in Xpot remain unknown. We have performed a combination of classical all-atom and accelerated molecular dynamics simulations on a set of complexes involving Xpot to study a range of features including conformational flexibility of free and cargo-bound Xpot and functionally critical contacts between Xpot and its cargo. The systems investigated include free Xpot and its different complexes, bound either to Ran (GTP/GDP) or tRNA or both. This approach provided a statistically reliable estimate of structural dynamics of Xpot after cargo release. The mechanistic basis for Xpot opening after cargo release has been explained in terms of dynamic structural hinges, about which neighboring region could be displaced to facilitate the nuclear to cytosolic state transition. Post-RanGTP hydrolysis, a cascade of events including local conformational change in RanGTP and loss of critical contacts at Xpot/tRNA interface suggest factors responsible for eventual release of tRNA. The level of flexibility in different Xpot complexes varied depending on the arrangement of individual HEAT repeats. Current study provides one of the most comprehensive and robust analysis carried out on this protein using molecular dynamics schemes.

Long-period modulated structure and electric-field-induced structural transformation in Na0.5Bi0.5TiO3-based lead-free piezoelectrics

Na0.5Bi0.5TiO3- based lead-free piezoelectrics exhibiting giant piezostrain are technologically interesting materials for actuator applications. The lack of clarity with regard to the structure of the nonpolar phase of this system has hindered the understanding of the structural mechanism associated with the giant piezostrain and other related phenomena. In this paper, we have investigated the structure and field-induced phase transformation behavior of a model system (0.94 - x) Na0.5Bi0.5TiO3-0.06BaTiO(3)-xK(0.5)Na(0.5)NbO(3) (0.0 <= x <= 0.025). A detailed structural analysis using neutron powder diffraction revealed that the nonpolar phase is neither cubic nor a mixture of rhombohedral (R3c) and tetragonal (P4bm) phases as commonly reported in literature but exhibits a long-period modulated structure, which is most probably of the type root 2 x root 2 x n with n = 16. Our results suggest that the giant piezoelectric strain is associated with a field-induced phase transformation of the long-period modulated structure to rhombohedral R3c structure above a critical field. We also demonstrate that the giant piezostrain is lost if the system retains a fraction of the field-induced R3c phase. A possible correlation among depolarization temperature, giant piezostrain, and its electrical fatigue behavior has also been indicated.