Chiral synthons from carvone .20. Stereo- and enantiospecific total synthesis of (-)-valeranone

Stereo- and enantiospecific total synthesis of the irregular sesquiterpene, valeranone, starting from S-6-methylcarvone employing a hydrindanone to decalone ring expansion methodology, is described.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nucleation and growth characteristics of cavities during the early stages of tensile creep deformation in a superplastic zirconia-20 wt% alumina composite

Constant-stress tensile creep experiments on a superplastic 3-mol%-yttria-stabilized tetragonal zirconia composite with 20 wt% alumina revealed that cavities nucleate relatively early during tensile deformation. The number of cavities nucleated increases with increasing imposed stress. The cavities nucleate at triple points associated largely with an alumina grain, and then grow rapidly in a cracklike manner to attain dimensions on the order of the grain facet size. It is suggested that coarser-grained superplastic ceramics exhibit lower ductility due to the ease in formation of such grain boundary facet-cracks and their interlinkage to form a macroscopic crack of critical dimensions.

Influence of synthesis route on structural phase transition in YBa2−xLaxCu3Oy (020)

The compounds YBa2−xLaxCu3Oy, with compositions (020), have been synthesised by nitrate decomposition method and solid-state reaction and characterised. Structural transition from orthorhombic to tetragonal phase occurred at (0.1520) in compounds synthesised by nitrate decomposition method, whereas no transition was observed in compounds synthesised by solid-state reaction for x values up to 0.20. The ternary phase formation temperature is influenced by the starting materials used and ionic size considerations. These factors are shown to determine the composition at which the changeover from orthorhombic (superconducting) to tetragonal (non-superconducting) phase transition (O–T transition) occurs.

Signature of a silver phase percolation threshold in microscopically phase separated ternary Ge0.15Se0.85-xAgx (0≤x≤0.20) glasses

Temperature modulated alternating differential scanning calorimetric studies show that Se rich Ge0.15Se0.85−xAgx (0 x 0.20) glasses are microscopically phase separated, containing Ag2Se phases embedded in a Ge0.15Se0.85 backbone. With increasing silver concentration, Ag2Se phase percolates in the Ge–Se matrix, with a well-defined percolation threshold at x = 0.10. A signature of this percolation transition is shown up in the thermal behavior, as the appearance of two exothermic crystallization peaks. Density, molar volume, and microhardness measurements, undertaken in the present study, also strongly support this view of percolation transition. The superionic conduction observed earlier in these glasses at higher silver proportions is likely to be connected with the silver phase percolation.

Thermodynamic, Raman and electrical switching studies on Si15Te85-xAgx (4 <= x <= 20) glasses

We have investigated thermal properties of bulk Si15Te85-xAgx (4 <= x <= 20) glasses in detail, through alternating differential scanning calorimetry experiments. The composition dependence of thermal parameters reveal the signatures of rigidity percolation and chemical threshold at compositions x = 12 and x = 19, respectively. The stability and glass forming ability of these glasses have also been determined using the data obtained from different thermodynamic quantities and it is found that the Si15Te85-xAgx glasses in the region 12 <= x <= 17 are more stable when compared to other glasses of the same series. Further, the blueshift observed in Raman spectroscopy investigations, in the composition range 12 <= x <= 13, support the occurrence of stiffness threshold in this composition range. All Si15Te85-xAgx (4 <= x <= 20) glasses are found to exhibit memory type switching (for sample thickness 0.25 mm) in the input current range 3-9 mA. The effect of rigidity percolation and chemical thresholds on switching voltages are observed at x = 12 and 19, respectively. (C) 2012 American Institute of Physics. [doi:10.1063/1.3682759]

Monsoon circulation interaction with Western Ghats orography under changing climate - Projection by a 20-km mesh AGCM

In this study, the authors have investigated the likely future changes in the summer monsoon over the Western Ghats (WG) orographic region of India in response to global warming, using time-slice simulations of an ultra high-resolution global climate model and climate datasets of recent past. The model with approximately 20-km mesh horizontal resolution resolves orographic features on finer spatial scales leading to a quasi-realistic simulation of the spatial distribution of the present-day summer monsoon rainfall over India and trends in monsoon rainfall over the west coast of India. As a result, a higher degree of confidence appears to emerge in many aspects of the 20-km model simulation, and therefore, we can have better confidence in the validity of the model prediction of future changes in the climate over WG mountains. Our analysis suggests that the summer mean rainfall and the vertical velocities over the orographic regions of Western Ghats have significantly weakened during the recent past and the model simulates these features realistically in the present-day climate simulation. Under future climate scenario, by the end of the twenty-first century, the model projects reduced orographic precipitation over the narrow Western Ghats south of 16A degrees N that is found to be associated with drastic reduction in the southwesterly winds and moisture transport into the region, weakening of the summer mean meridional circulation and diminished vertical velocities. We show that this is due to larger upper tropospheric warming relative to the surface and lower levels, which decreases the lapse rate causing an increase in vertical moist static stability (which in turn inhibits vertical ascent) in response to global warming. Increased stability that weakens vertical velocities leads to reduction in large-scale precipitation which is found to be the major contributor to summer mean rainfall over WG orographic region. This is further corroborated by a significant decrease in the frequency of moderate-to-heavy rainfall days over WG which is a typical manifestation of the decrease in large-scale precipitation over this region. Thus, the drastic reduction of vertical ascent and weakening of circulation due to `upper tropospheric warming effect' predominates over the `moisture build-up effect' in reducing the rainfall over this narrow orographic region. This analysis illustrates that monsoon rainfall over mountainous regions is strongly controlled by processes and parameterized physics which need to be resolved with adequately high resolution for accurate assessment of local and regional-scale climate change.

Densification mechanisms during hot pressing of ZrB2-20 vol.% SiC composite

The dominant densification mechanisms for hot pressing of ZrB2-20 vol.% SiC composite at different hot-pressing temperatures and pressures was identified. The dominant densification mechanisms were found to change over a very short temperature range. For hot pressing at 1700 degrees C, the dominant densification mechanism was found to be mechanically driven particle fragmentation and rearrangement only, whereas at 1850 degrees C a plastic flow mechanism started to become dominant after initial particle fragmentation and rearrangement. At 2000 degrees C, the dominant mechanism changed from plastic flow to grain boundary diffusion. (c) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Temperature dependent magnetic ordering and electrical transport behavior of nano zinc ferrite from 20 to 800 K

The nano ZnFe2O4 compound was prepared by eco-friendly hydrothermal method. The characterization of the sample for its structure, morphology and composition were done by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dynamic light scattering, Fourier transform infrared spectroscopy, zeta surface profiler and UV-Visible spectroscopy studies. The PXRD measurement reveals that the compound shows spinel cubic phase belong Fd (3) over barm (227) space group. Morphology of the compound from SEM and surface profile shows nearly spherical agglomerated particles with well defined grains and grain boundaries. The material shows the semiconducting behavior with E-g of 2.3 eV at room temperature (RT). The variation in the magnetic ordering was observed for wide range of temperature. The compound behaves like a soft magnetic material with ferrimagnetic at various temperatures except at RT. Both magnetic and EPR studies supports the superparamagnetic behavior of the the sample. The DC conductivity, dielectric and AC conductivity behavior of the 1000 degrees C pellets sintered for 2 h shows good frequency dependent transport properties. The present study facilitate in selecting the suitable materials for the nanoelectronics and spintronic applications. (C) 2013 Elsevier B.V. All rights reserved.

Conformational Analysis of a 20-Membered Cyclic Peptide Disulfide from Conus virgo with a WPW Segment: Evidence for an Aromatic-Proline Sandwich

A novel peptide containing a single disulfide bond, CIWPWC (Vi804), has been isolated and characterised from the venom of the marine cone snail, Conus virgo. A precursor polypeptide sequence derived from complementary DNA, corresponding to the M-superfamily conotoxins, has been identified. The identity of the synthetic and natural peptide sequence has been established. A detailed analysis of the conformation in solution is reported for Vi804 and a synthetic analogue, (CIWPWC)-W-D ((D)W3-Vi804), in order to establish the structure of the novel WPW motif, which occurs in the context of a 20-membered macrocyclic disulfide. Vi804 exists exclusively in the cis W3P4 conformer in water and methanol, whereas (D)W3-Vi804 occurs exclusively as the trans conformer. NMR spectra revealed a W3P4 typeVI turn in Vi804 and a typeII turn in the analogue peptide, (D)W3-Vi804. The extremely high-field chemical shifts of the proline ring protons, together with specific nuclear Overhauser effects, are used to establish a conformation in which the proline ring is sandwiched between the flanking Trp residues, which emphasises a stabilising role for the aromatic-proline interactions, mediated predominantly by dispersion forces.

Evolution of deformation texture and magnetic properties in a nanocrystalline nickel-20 wt% cobalt alloy

The evolution of crystallographic texture in a nanocrystalline nickel-20 wt% cobalt alloy has been investigated for deformation up to large strains. The effect of texture on magnetic properties has been evaluated. The material shows characteristic copper-type texture at large strain levels. Microstructural examinations indicate that the evolution of texture is assisted by deformation-induced grain growth. The values of saturation magnetization and coercivity have been correlated with the crystallographic texture and grain size. (C) 2014 Elsevier B.V. All rights reserved.

Ligand 5,10,15,20-Tetra(N-methyl-4-pyridyl)porphine (TMPyP4) Prefers the Parallel Propeller-Type Human Telomeric G-Quadruplex DNA over Its Other Polymorphs

The binding of ligand 5,10,15,20-tetra(N-methyl-4-pyridyl)porphine (TMPyP4) with telomeric and genomic G-quadruplex DNA has been extensively studied. However, a comparative study of interactions of TMPyP4 with different conformations of human telomeric G-quadruplex DNA, namely, parallel propeller-type (PP), antiparallel basket-type (AB), and mixed hybrid-type (MH) G-quadruplex DNA, has not been done. We considered all the possible binding sites in each of the G-quadruplex DNA structures and docked TMPyP4 to each one of them. The resultant most potent sites for binding were analyzed from the mean binding free energy of the complexes. Molecular dynamics simulations were then carried out, and analysis of the binding free energy of the TMPyP4-G-quadruplex complex showed that the binding of TMPyP4 with parallel propeller-type G-quadruplex DNA is preferred over the other two G-quadruplex DNA conformations. The results obtained from the change in solvent excluded surface area (SESA) and solvent accessible surface area (SASA) also support the more pronounced binding of the ligand with the parallel propeller-type G-quadruplex DNA.

Structural Evolution and Property Changes in Nd_{60}Al_{10}Fe_{20}Co_{10} Bulk Metallic Glass During Crystallization

The structural evolution and property changes in Nd60Al10Fe20Co10 bulk metallic glass (BMG) upon crystallization are investigated by the ultrasonic method, x-ray diffraction, density measurement, and differential scanning calorimetry. The elastic constants and Debye temperature of the BMG are obtained as a function of annealing temperature. Anomalous changes in ultrasonic velocities, elastic constants, and density are observed between 600–750 K, corresponding to the formation of metastable phases as an intermediate product in the crystallization process. The changes in acoustic velocities, elastic constants, density, and Debye temperature of the BMG relative to its fully crystallized state are much smaller, compared with those of other known BMGs, the differences being attributed to the microstructural feature of the BMG.