Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Insights into the Substrate Specificity of a Thioesterase Rv0098 of Mycobacterium Tuberculosis through X-ray Crystallographic and Molecular Dynamics Studies

The crystal structure of Rv0098, a long-chain fatty acyl-CoA thioesterase from Mycobacterium tuberculosis with bound dodecanoic acid at the active site provided insights into the mode of substrate binding but did not reveal the structural basis of substrate specificities of varying chain length. Molecular dynamics studies demonstrated that certain residues of the substrate binding tunnel are flexible and thus modulate the length of the tunnel. The flexibility of the loop at the base of the tunnel was also found to be important for determining the length of the tunnel for accommodating appropriate substrates. A combination of crystallographic and molecular dynamics studies thus explained the structural basis of accommodating long chain substrates by Rv0098 of M. tuberculosis.

Growth mechanism of the Nb(X)Si-2 and [Nb(X)](5)Si-3 phases by reactive diffusion in Nb (X = Ti, Mo, or Zr)-Si systems

The effects of Mo, Ti, and Zr on the diffusion and growth of the Nb(X)Si-2 and Nb(X)(5)Si-3 phases in an Nb(X)-Si system are analyzed. The integrated diffusion coefficients are determined from diffusion couple experiments and compared with the data previously calculated in a binary Nb-Si system. The growth rates of both phases are affected by the addition of Mo and Zr, whereas the addition of Ti has no effect. The atomic mechanism of diffusion is also discussed based on the crystal structure and the possible changes in the defect concentrations due to alloying. Finally, the growth mechanism of the phases is discussed on the basis of a physico-chemical approach. (C) 2011 Elsevier Ltd. All rights reserved.

Structure and Photocatalytic Activity of Ti 1- x M x O 2±δ (M = W, V, Ce, Zr, Fe, and Cu) Synthesized by Solution Combustion Method

The W, V, Ce, Zr, Fe, and Cu metal ion substituted nanocrystalline anatase TiO2 was prepared by solution combustion method and characterized by XRD, Raman, BET, EPR, XPS, IR TGA, UV absorption, and photoluminescence measurements. The structural studies indicate that the solid solution formation was limited to a narrow range of concentrations of the dopant ions. The photocatalytic degradation of 4-nitrophenol under UV and solar exposure was investigated with Ti1-xMxO2±δ. The degradation rates of 4-nitrophenol with these catalysts were lesser than the degradation rates of 4-nitrophenol with undoped TiO2 both with UV exposure and solar radiation. However, the photocatalytic activities of most metal ion doped TiO2 are higher than the activity of the commercial TiO2, Degussa P25. The decrease in photocatalytic activity is correlated with decrease in photoluminescence due to electron states of metal ions within the band gap of TiO2.

Neutron scattering study of combustion-synthesized Ce1−xCuxO2−x

Powder neutron di®raction and Hi-Q neutron di®raction data have been recorded and analysed in order to obtain the local and long range order of Cu in Cu-doped CeO2 with three doping levels of Cu. Rietveld method and MCGR techniques of data analysis for the two types of data reveal that the Cu ion is in the 2+ oxidation state and has a vacancy in its ¯rst coordination shell. These deductions from the data analysis ¯t well with the mechanism of catalysis we propose.

Transport, optical and magnetotransport properties of hetero-epitaxial InAsxSb1−x/GaAs(x0.06) and bulk View the MathML source crystals: experiment and theoretical analysis

We briefly review the growth and structural properties of View the MathML source bulk single crystals and View the MathML source epitaxial films grown on semi-insulating GaAs substrates. Temperature-dependent transport measurements on these samples are then correlated with the information obtained from structural (XRD, TEM, SEM) and optical (FTIR absorption) investigations. The temperature dependence of mobility and the Hall coefficient are theoretically modelled by exactly solving the linearized Boltzmann transport equation by inversion of the collision matrix and the relative role of various scattering mechanisms in limiting the low temperature and View the MathML source mobility is estimated. Finally, the first observation of Shubnikov oscillations in InAsSb is discussed.

Growth of InSb(1-x)Bix crystals by Rotatary Bridgman method and their characterization

The Rotatary Bridgman method was used to grow ternary InSb(1-x)SBix, crystals. In this method the ampoule was subjected to reversible rotation at a rate of 60rpm. High quality crystals of 8mm diameter and 25mm length were grown with 6.5 atomic percentage of Bi. The grown crystals were characterized employing various techniques such as energy dispersive spectroscopy, x-ray diffraction, differential scanning calorimetery, infrared spectroscopy and Hall measurement.

Band-Structure Lineup at In0.2Ga0.8N/Si Heterostructures by X-ray Photoelectron Spectroscopy

In0.2Ga0.8N layers were directly grown on Si(111) substrate by plasma-assisted molecular beam epitaxy (PAMBE). Structural characteristics of the as-grown InGaN epilayers were evaluated high resolution X-ray diffraction and composition of InGaN was estimated from photoluminescence spectra using the standard Vegard's law. High-resolution X-ray photoemission spectroscopy measurements were used to determine the band offset of wurtzite-In0.2Ga0.8N/Si(111) heterojunctions. The valence band of InGaN is found to be 2.08 +/- 0.04 eV below that of Si. The conduction band offset (CBO) of InGaN/Si heterojunction is found similar to 0.74 eV and a type-II heterojunction. (C) 2012 The Japan Society of Applied Physics

Synthesis, spectroscopic properties and biological evaluation of transition metal complexes of salicylhydrazone of anthranilhydrazide: X-ray crystal structure of copper complex

The transition metal complexes of salicylhydrazone of anthranilhydrazide (H2L) were synthesised. The structures of metal complexes were characterized by various spectroscopic [IR, NMR, UV-Vis, EPR], thermal and other physicochemical methods. The single-crystal X-ray diffraction study of [Cu(HL)Cl]center dot H2O reveal its orthorhombic system with space group P2(1)2(1)2 and Z=4. The copper center has a distorted square planar geometry with ONO and Cl as the donor atoms. The ligand and its metal chelates have been screened for their antimicrobial and anti-tubercular activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand and in few cases better than the standard used. Among the bacterial strains used, the complexes are highly potent against Gram-positive strains compared to Gram-negative. Anti-tubercular activity exhibited by the Co(II) complex is comparable with the standard used. (C) 2011 Elsevier B. V. All rights reserved.

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]

Determination of MBE grown wurtzite GaN/Ge3N4/Ge heterojunctions band offset by X-ray photoelectron spectroscopy

Hexagonal Ge3N4 layer was prepared on Ge surface by in situ direct atomic source nitridation and it is promising buffer layer to grow GaN on Ge (111). The valence band offset (VBO) of GaN/Ge3N4/Ge heterojunctions is determined by X-ray photoemission spectroscopy. The valence band (VB) of Ge3N4 is found to be 0.38?+/-?0.04?eV above the GaN valance band and 1.14?+/-?0.04?eV below the Ge. The GaN/Ge3N4 and Ge3N4/Ge are found type-II and type-I heterojunctions, respectively. The exact measurements of the VBO and conduction band offset (CBO) are important for use of GaN/Ge3N4/Ge (111) heterosystems.

Tuning of phonon anharmonicity in pyrochlore titanates: temperature-dependent Raman studies of Sm2Ti2-xZrxO7 (x=0, 1/2, 3/4, and 2)and stuffed spin-ice Ho2+xTi2-xO7-x/2 (x=0, 1/3, and 2/3)

Anomalous temperature dependence of Raman phonon wavenumbers attributed to phononphonon anharmonic interactions has been studied in two different families of pyrochlore titanates. We bring out the role of the ionic size of titanium and the inherent vacancies of pyrochlore in these anomalies by studying the effect of replacement of Ti4?+ by Zr4?+ in Sm2Ti2O7 and by stuffing Ho3?+ in place of Ti4?+ in Ho2Ti2O7 with appropriate oxygen stoichiometry. Our results show that an increase in the concentration of the larger ion, i.e. Zr4?+ or Ho3?+, reduces the phonon anomalies, thus implying a decrease in the phononphonon anharmonic interactions. In addition, we find signatures of coupling between a phonon and crystal field transition in Sm2Ti2O7, manifested as an unusual increase in the phonon intensity with increasing temperature. Copyright (c) 2011 John Wiley & Sons, Ltd.

Hardness and Nitrogen Bonding Structure of A(x)Ti(1-x)N/CrN Multilayer Hard Coating

AlxTi1-xN/CrN multilayer coatings were fabricated by magnetron sputtering and those hardness variations were studied by observing the crack propagation and measuring the chemical bonding state of nitrides by Ti addition. While AlN/CrN multilayer shown stair-like crack propagation, AlxTi1-xN/CrN multilayer illustrated straight crack propagation. Most interestingly, Ti addition induced more broken nitrogen bonds in the nitride multilayers, leading to the reduction of hardness. However, the hardness of Al0.25Ti0.75N/CrN multilayer, having high Ti contents, increased by the formation of many Ti-N bond again instead of Al-N bond. From these results, we found that linear crack propagation behavior was dominated by broken nitrogen bonds in the AlxT1-xN/CrN multilayer coatings.

Sivers effect and transverse single spin asymmetry in e+p(up arrow) -> e+J/psi+X

We discuss the possibility of using electroproduction of J/psi as a probe of gluon Sivers function by measuring single spin asymmetry (SSA) in experiments with transversely polarized protons and electron beams. We estimate SSA for JLab, HERMES, COMPASS, and eRHIC energies using the color evaporation model of charmonium production and find asymmetry up to 25% for certain choices of model parameters which have been used earlier for estimating SSA in the SIDIS and Drell-Yan processes.

Tuning the magnetic ground state in LixNi(2-x)O2

The experimental determination of the magnetic ground state of triangular lattice anti-ferromagnet LiNiO2 is an intriguing problem as the system is prone to be Li deficient. We have been successful in preparing nearly stoichiometric LiNiO2 showing an anti-ferromagnetic ground state with an ordering temperature similar to 12 K. As the Li deficiency increases the sample exhibits spin glass behavior evidenced by a shift in the spin glass freezing temperature as a function of frequency in the ac susceptibility studies. As the Li deficiency crosses a critical limit, the sample becomes ferromagnetic in nature. We are able to tune the ferromagnetic transition temperature up to 240 K by varying the Li content. Finally, we have constructed a magnetic phase diagram. (C) 2012 American Institute of Physics. doi:10.1063/1.3675997]