Systematic crystallographic investigation of hydrogen-bonded networks involving monohydrogen tartrate-amine complexes: Potential materials for nonlinear optics

Crystal structures of six binary salts involving aromatic amines as cations and hydrogen tartrates as anions are presented. The materials are 2,6-xylidinium-L-monohydrogen tartrate monohydrate, C12H18O6.5N, P22(1)2(1), a = 7.283(2) Angstrom, b = 17.030(2) Angstrom, c = 22.196(2) Angstrom, Z = 8; 2,6-xylidinium-D-dibenzoyl monohydrogen tartrate, C26H25O8N, P2(1), a = 7.906(1) Angstrom, b = 24.757(1) Angstrom, c = 13.166(1) Angstrom, beta = 105.01(1)degrees, Z = 4; 2,3-xylidinium-D-dibenzoyl monohydrogen tartrate monohydrate, C26H26O8.5N, P2(1), a = 7.837(1) Angstrom, b = 24.488(1) Angstrom, c = 13.763(1) Angstrom, beta = 105.69(1)degrees, Z = 4; 2-toluidinium-D-dibenzoyl monohydrogen tartrate, C25H23O8N, P2(1)2(1)2(1), a = 13.553(2) Angstrom, b = 15.869(3) Angstrom, c = 22.123(2) Angstrom, Z = 8; 3-toluidinium-D-dibenzoyl monohydrogen tartrate (1:1), C25H23O8N, P1, a = 7.916(3) Angstrom, b = 11.467(6) Angstrom, c = 14.203(8) Angstrom, alpha = 96.44(4)degrees, beta = 98.20(5)degrees, = 110.55(5)degrees, Z = 2; 3-toluidinium-D-dibenzoyl tartrate dihydrate (1:2), C32H36O10N, P1, a = 7.828(3) Angstrom, b = 8.233(1) Angstrom, c = 24.888(8) Angstrom, alpha = 93.98 degrees, beta = 94.58(3)degrees, = 89.99(2)degrees, Z = 2. An analysis of the hydrogen-bonding schemes in terms of crystal packing, stoichiometric variations, and substitutional variations in these materials provides insights to design hydrogen-bonded networks directed toward the engineering of crystalline nonlinear optical materials.

Studies in crystal engineering: Crystal packing, topological photodimerization and structure-reactivity correlations in fluoro-substituted styrylcoumarins

In continuation of our studies on the influence of fluoro substitution on the solid state photobehaviour and packing pattern of styrylcoumarins, the results obtained for 4-(3-fluorostyryl)coumarin 1, 4-styryl-6-fluorocoumarin 2 and 4-styryl-7-fluorocoumarin 3 are presented. The configuration of the dimers was established on the basis of crystal packing of 1 and 2 (alpha-packed). A rationale for the significantly lower dimer yield in the crystal for 2 is proposed. In the observed centrosymmetric arrangement of the reactants the C=O ...pi (phenyl) contacts seem to provide additional attractive interactions. C-H ... O and C-H ... F hydrogen bonding seems to provide stability in these structures.

Nonlinear optical activity of anhydrous and hydrated sodium p-nitrophenolate

Differently hydrated sodium p-nitrophenolate (NPNa) crystals were obtained while growing them from different solvents such as methanol and water. Thermal analysis and powder X-ray diffraction studies were carried out on these crystals. Kurtz powder SHG technique was used for qualitative assessment of their nonlinear optical (NLO) activity. From the detailed single-crystal X-ray diffraction studies it is established that NPNa has three different forms, of which only one is found to possess NLO activity. Additionally, a new NLO active crystal was also found to grow from aqueous solution. (C) 1999 Elsevier Science B.V. All rights reserved.

The influence of temperature gradient and lowering speed on the melt-solid interface shape of GaxIn1-xSb alloy crystals grown by vertical Bridgman technique

Radially homogeneous bulk alloys of GaxIn1-xSb in the range 0.7 < x < 0.8, have been grown by vertical Bridgman technique. The factors affecting the interface shape during the growth were optimised to achieve zero convexity. From a series of experiments, a critical ratio of the temperature gradient (G) of the furnace at the melting point of the melt composition to the ampoule lowering speed (v) was deduced for attaining the planarity of the melt-solid interface. The studies carried out on directional solidification of Ga0.77In0.23Sb mixed crystals employing planar melt-solid interface exhibited superior quality than those with nonplanar interfaces. The solutions to certain problems encountered during the synthesis and growth of the compound were discussed. (C) 1999 Elsevier Science B.V. All rights reserved.

Electronic structure of In1-xMnxAs studied by photoemission spectroscopy: Comparison with Ga1-xMnxAs

We have investigated the electronic structure of the p-type diluted magnetic semiconductor In1-xMnxAs by photoemission spectroscopy. The Mn 3d partial density of states is found to be basically similar to that of Ga1-xMnxAs. However, the impurity-band-like states near the top of the valence band have not been observed by angle-resolved photoemission spectroscopy unlike Ga1-xMnxAs. This difference would explain the difference in transport, magnetic and optical properties of In1-xMnxAs and Ga1-xMnxAs. The different electronic structures are attributed to the weaker Mn 3d-As 4p hybridization in In1-xMnxAs than in Ga1-xMnxAs.

Essential dynamics and sidechain hydrogen bond cluster studies on eosinophil cationic protein

Eosinophil Cationic Protein (ECP) is a member of RNase A superfamily which carries out the obligatory catalytic role of cleaving RNA. It is involved in a variety of biological functions. Molecular dynamics simulations followed by essential dynamics analysis on this protein are carried out with the goal of gaining insights into the dynamical properties at atomic level. The top essential modes contribute to subspaces and to the transition phase. Further, the sidechain-sidechain/sidechain-mainchain hydrogen bond clusters are analyzed in the top modes, and compared with those of crystal structure. The role of residues identified by these methods is discussed in the context of concerted motion, structure and stability of the protein.

Longwave radiative forcing of Indian Ocean tropospheric aerosol

A spectrally resolved discrete-ordinates radiative transfer model is used to calculate the change in downwelling surface and top-of-the-atmosphere (TOA) outgoing longwave (3.9-500 mum) radiative fluxes induced by tropospheric aerosols of the type observed over the Indian Ocean during the Indian Ocean Experiment (INDOEX). Both external and internal aerosol mixtures were considered. Throughout the longwave, the aerosol volume extinction depends more strongly on relative humidity than in most of the shortwave (0.28-3.9 mum), implying that particle growth factors and realistic relative humidity profiles must be taken into account when modeling the longwave radiative effects of aerosols. A typical boundary layer aerosol loading, with a 500-nm optical depth of 0.3, will increase the downwelling longwave flux at the surface by 7.7 W m(-2) over the clean air case while decreasing the outgoing longwave radiation by 1.3 W m(-2). A more vertically extended aerosol loading, exhibiting a high opacity plume between 2 and 3 km above the surface and having a typical 500-nm optical depth of 0.7, will increase the downwelling longwave flux at the surface by 11.2 W m(-2) over the clean air case while decreasing the outgoing longwave radiation by 2.7 W m(-2). For a vertically extended aerosol profile, approximately 30% of the TOA radiative forcing comes from sea salt and approximately 60% of the forcing comes from the combination of sea salt and dust. The remaining forcing is from anthropogenic constituents. These results are for the external mixture. For an internal mixture, TOA longwave forcings can be up to a factor of two larger. Therefore, to complete our understanding of this region's longwave aerosol radiative properties, more detailed information is needed about aerosol mixing states. These longwave radiative effects partially offset the large shortwave aerosol radiative forcing and should be included in regional and global climate modeling simulations.

Phenobarbitone-mediated translocation of the cytosolic proteins interacting with the 5 '-proximal region of rat liver CYP2B1/B2 gene into the nucleus

The positive element (PE) (-69 to -98 bp) within the 5'-proximal region of the CYP2B1B2 gene (+1 to -179 bp) of rat liver is essential for phenobarbitone (PB) response and gives a single major complex with the rat liver cytosol in gel shift analysis. This complex corresponds to complex I (top) of the three complexes given by the nuclear extracts. PB treatment of rats leads to a decrease in complex I formation with the cytosol and PE and an increase in the same with the nuclear extract in gel shift analysis. Both the changes are counteracted by simultaneous okadaic acid administration. The nuclear protein giving rise to complex I has been isolated and has an M-r of 26 kDa. The cytosolic counterpart consists of two species, 26 and 28 kDa, as revealed by Southwestern blot analysis using labeled PE. It is concluded that PB treatment leads to the translocation accompanied by processing of the cytosolic protein species into the nucleus that requires protein dephosphorylation. It is suggested that PB may exert a global regulation on the transcription of many genes by modulating the phosphorylation status of different protein factors involved in transcriptional regulation. (C) 2002 Elsevier Science (USA).

Growth and characterization of ferroelectric glycine phosphite single crystals

Single crystals of a recent ferroelectric material, glycine phosphite were grown from aqueous solution employing the techniques of slow cooling and controlled evaporation. Powder X-ray diffraction studies as well as thermal analysis were carried out on the grown crystals. The morphology of the crystal has been determined using contact and optical goniometry. The mechanical hardness of the crystal was evaluated by Vickers indentation method. Thickness dependence of the dielectric properties has been investigated and the results can be interpreted in terms of a surface layer of lower dielectric constant.

Characterization of Ni-Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni-Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H2SO4 medium. Electronic absorption spectrum of bath solution containing Ni2+ Pd2+ ions and EDA indicated the formation of a four coordinate square planar metal-ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd-Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm(-2)). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H2SO4 medium is found to be promoted on Ni-Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni-Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times. (C) 2003 Elsevier Science B.V. All rights reserved.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Influences of the springtime northern Indian biomass burning over the central Himalayas

The influences of the springtime northern Indian biomass burning are shown for the first time over the central Himalayas by using three years (2007-2009) of surface and space based observations along with a radiative transfer model. Near-surface ozone, black carbon (BC), spectral aerosol optical depths (AODs) and the meteorological parameters are measured at a high altitude site Nainital (29.37 degrees N, 79.45 degrees E, 1958 m amsl) located in the central Himalayas. The satellite observations include the MODIS derived fire counts and AOD (0.55 mu m), and OMI derived tropospheric column NO(2), ultraviolet aerosol index and single scattering albedo. MODIS fire counts and BC observations are used to identify the fire-impacted periods (372 h during 2007-2009) and hence the induced enhancements in surface BC, AOD (0.5 mu m) and ozone are estimated to be 1802 ng m(-3) (similar to 145%), 0.3 (similar to 150%) and 19 ppbv (similar to 34%) respectively. Large enhancements (53-100%) are also seen in the satellite derived parameters over a 2 degrees x 2 degrees region around Nainital. The present analysis highlights the northern Indian biomass burning induced cooling at the surface (-27 W m(-2)) and top of the atmosphere (-8 W m(-2)) in the lesser polluted high altitude regions of the central Himalayas. This cooling leads to an additional atmospheric warming of 19 W m(-2) and increases the lower atmospheric heating rate by 0.8 K day(-1). These biomass burning induced changes over the central Himalayan atmosphere during spring may also lead to enhanced short-wave absorption above clouds and might have an impact on the monsoonal rainfall.

Interaction anisotropy and shear instability of aspirin polymorphs established by nanoindentation

Nanoindentation is applied to the two polymorphs of aspirin to examine and differentiate their interaction anisotropy and shear instability. Aspirin provides an excellent test system for the technique because: (i) polymorphs I and II exhibit structural similarity in two dimensions, thereby facilitating clear examination of the differences in mechanical response in relation to well-defined differences between the two crystal structures; (ii) single crystals of the metastable polymorph II have only recently become accessible; (iii) shear instability has been proposed for II. Different elastic moduli and hardness values determined for the two polymorphs are correlated with their crystal structures, and the interpretation is supported by measured thermal expansion coefficients. The stress-induced transformation of the metastable polymorph II to the stable polymorph I can be brought about rapidly by mechanical milling, and proceeds via a slip mechanism. This work establishes that nanoindentation provides ``signature'' responses for the two aspirin polymorphs, despite their very similar crystal structures. It also demonstrates the value of the technique to quantify stability relationships and phase transformations in molecular crystals, enabling a deeper understanding of polymorphism in the context of crystal engineering.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Growth of silicon nanowires by electron beam evaporation using indium catalyst

For the first time silicon nanowires have been grown on indium (In) coated Si (100) substrates using e-beam evaporation at a low substrate temperature of 300 degrees C. Standard spectroscopic and microscopic techniques have been employed for the structural, morphological and compositional properties of as grown Si nanowires. The as grown Si nanowires have randomly oriented with an average length of 600 nm for a deposition time of 15 min. As grown Si nanowires have shown indium nanoparticle (capped) on top of it confirming the Vapor Liquid Solid (VLS) growth mechanism. Transmission Electron Microscope (TEM) measurements have revealed pure and single crystalline nature of Si nanowires. The obtained results have indicated good progress towards finding alternative catalyst to gold for the synthesis of Si nanowires. (C) 2011 Elsevier B.V. All rights reserved.