Synthesis and characterization of metal substituted AlxCr1-x(acetylacetonate)(3) single-source precursors for their application to MOCVD of thin films

A detailed study, involving the synthesis of a single-source precursor containing two metal ions sharing the same crystallographic site, has been undertaken to elucidate the use of such a single-source precursor in a CVD process for growing thin films of oxides comprising these two metals, ensuring a uniform composition and distribution of metal ions. The substituted complexes Cr1-xAlx(acac)(3), where acac = acetyl-acetonate, have been prepared by a co-synthesis method, and characterized using UV-Vis spectroscopy. TGA/DTA measurements, and single crystal X-ray diffraction at low temperature. All the studied compositions crystallize in the monoclinic space group P2(1)/c with Z = 4 in the unit cell. It was observed that the ratio (Al:Cr) of the site occupancy for the metal ions, obtained from single crystal refinement, is in agreement with the results obtained from complexometric titrations. All the solid state structures have the metal in an octahedral environment forming six-membered chelate rings. M-O acac bond lengths and disorder in the terminal carbon have been studied in detail for these substituted metal-organic complexes. One composition among these was chosen to evaluate their suitability as a single-source precursor in a LPMOCVD process (low-pressure metal-organic chemical vapour deposition) for the deposition of a substituted binary metal oxide thin film. The resulting thin films were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. (C) 2010 Elsevier Ltd. All rights reserved.

A study on the formation of crystalline phases during solidification and crystallisation in the bulk metallic glass of Zr53Cu21Al10Ni8Ti8 composition

The present paper considers the formation of crystalline phases during solidification and crystallisation of the Zr53Cu21Al10Ni8Ti8 alloy. Solidification was carried out by a copper mould casting technique, which yielded a partially crystalline microstructure comprising a `big cube phase' in a dendritic morphology and a bct Zr2Ni phase. Detailed high-resolution microscopy was carried out to determine possible mechanisms for the formation of the crystalline phases. Based on microstructural examinations, it was established that the dendrites grew by the attachment of atomistic ledges. The bct Zr2Ni phase, formed during solidification and crystallisation, showed various types of faults depending on the crystallite size, and its crystallography was examined in detail. It has been shown that the presence of these faults could be explained by anti-site occupancy in the bct lattice of the Zr2Ni phase.

Structural and relaxor characteristics of Ca0.18Sr0.226Ba0.594Nb2O6

Polycrystalline Ca0.18Sr0.226Ba0.594Nb2O6 (CSBN18) was synthesized via the solid-state reaction route. X-ray structural studies confirmed it belonged to the tetragonal tungsten bronze family. Rietveld refinement of the X-ray data has been carried out for CSBN18 where the atomic positions and site occupancy factors for A-sites have been determined. The dielectric properties of CSBN18 ceramic were studied as a function of temperature in the 100 Hz - 1 MHz frequency range. The dielectric relaxation followed the Vogel-Fulcher relation wherein E-a = 37.4 meV; T-f = 131.5 degrees C and omega(0) = 4.31 x 10(9) rad s(-1). A high pyroelectric coefficient of similar to 250 mu C m(-2).K was obtained around the transition temperature (similar to 150 degrees C). This is significantly higher than that reported for polycrystalline SrxBa1-xNb2O6 (SBN). However, the piezoelectric coefficient (d(33)) of the title composition was as low as 6 pC N-1.

Divvying up an incubator: How parasitic and mutualistic fig wasps use space within their nursery microcosm

Differential occupancy of space can lead to species coexistence. The fig-fig wasp pollination system hosts species-specific pollinating and parasitic wasps that develop within galls in a nursery comprising a closed inflorescence, the syconium. This microcosm affords excellent opportunities for investigating spatial partitioning since it harbours a closed community in which all wasp species are dependent on securing safe sites inside the syconium for their developing offspring while differing in life history, egg deposition strategies and oviposition times relative to nursery development. We determined ontogenetic changes in oviposition sites available to the seven-member fig wasp community of Ficus racemosa comprising pollinators, gallers and parasitoids. We used species distribution models (SDMs) for the first time at a microcosm scale to predict patterns of spatial occurrence of nursery occupants. SDMs gave high true-positive and low false-positive site occupancy rates for most occupants indicating species specificity in oviposition sites. The nursery microcosm itself changed with syconium development and sequential egg-laying by different wasp species. The number of sites occupied by offspring of the different wasp species was negatively related to the risk of syconium abortion by the plant host following oviposition. Since unpollinated syconia are usually aborted, parasitic wasps ovipositing into nurseries at the same time as the pollinator targeted many sites, suggesting response to lower risk of syconium abortion owing to reduced risk of pollination failure compared to those species ovipositing before pollination. Wasp life history and oviposition time relative to nursery development contributed to the co-existence of nursery occupants.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

The X-ray photoelectron spectroscopy and high-temperature structural studies of Zn1-xNixO/NiO two-phase composites

Detailed investigation of the chemical states and local atomic environment of Ni and Zn in the two-phase composites of Zn1-xNixO/NiO was reported. The X-ray photoelectron spectra of both Ni-2p and Zn-2p revealed the existence of a doublet with spin-orbit splitting approximate to 17.9 and 23.2eV, respectively confirming the divalent oxidation state of both Ni and Zn. However, the samples fabricated under oxygen-rich conditions exhibit significant difference in the binding energy approximate to 18.75eV between the 2p3/2 and 2p1/2 states of Ni. The shift in the satellite peaks of Ni-2p with increasing the Ni composition x within the Zn1-xNixO/NiO matrix signifies the attenuation of nonlocal screening because of reduced site occupancy of two adjacent Zn ions. The temperature dependence of X-ray diffraction analysis reveals a large distortion in the axial-rhombohedral angle for oxygen-rich NiO. Conversely, no significant distortion was noticed in the NiO system present as a secondary phase within Zn1-xNixO. Nevertheless, the unit-cell volume of both wurtzite h.c.p. Zn1-xNixO and f.c.c. NiO exhibits an anomalous behavior between 150 and 300 degrees C. The origin of such unusual change in the unit-cell volume was discussed in terms of oxygen stoichiometry.

Three-Dimensional Site Characterization Model Using Artificial Neural Networks

This research is designed to develop a new technique for site characterization in a three-dimensional domain. Site characterization is a fundamental task in geotechnical engineering practice, as well as a very challenging process, with the ultimate goal of estimating soil properties based on limited tests at any half-space subsurface point in a site.In this research, the sandy site at the Texas A&M University's National Geotechnical Experimentation Site is selected as an example to develop the new technique for site characterization, which is based on Artificial Neural Networks (ANN) technology. In this study, a sequential approach is used to demonstrate the applicability of ANN to site characterization. To verify its robustness, the proposed new technique is compared with other commonly used approaches for site characterization. In addition, an artificial site is created, wherein soil property values at any half-space point are assumed, and thus the predicted values can compare directly with their corresponding actual values, as a means of validation. Since the three-dimensional model has the capability of estimating the soil property at any location in a site, it could have many potential applications, especially in such case, wherein the soil properties within a zone are of interest rather than at a single point. Examples of soil properties of zonal interest include soil type classification and liquefaction potential evaluation. In this regard, the present study also addresses this type of applications based on a site located in Taiwan, which experienced liquefaction during the 1999 Chi-Chi, Taiwan, Earthquake.

Influence of rock depth on seismic site classification for shallow bedrock regions

Seismic site classifications are used to represent site effects for estimating hazard parameters (response spectral ordinates) at the soil surface. Seismic site classifications have generally been carried out using average shear wave velocity and/or standard penetration test n-values of top 30-m soil layers, according to the recommendations of the National Earthquake Hazards Reduction Program (NEHRP) or the International Building Code (IBC). The site classification system in the NEHRP and the IBC is based on the studies carried out in the United States where soil layers extend up to several hundred meters before reaching any distinct soil-bedrock interface and may not be directly applicable to other regions, especially in regions having shallow geological deposits. This paper investigates the influence of rock depth on site classes based on the recommendations of the NEHRP and the IBC. For this study, soil sites having a wide range of average shear wave velocities (or standard penetration test n-values) have been collected from different parts of Australia, China, and India. Shear wave velocities of rock layers underneath soil layers have also been collected at depths from a few meters to 180 m. It is shown that a site classification system based on the top 30-m soil layers often represents stiffer site classes for soil sites having shallow rock depths (rock depths less than 25 m from the soil surface). A new site classification system based on average soil thickness up to engineering bedrock has been proposed herein, which is considered more representative for soil sites in shallow bedrock regions. It has been observed that response spectral ordinates, amplification factors, and site periods estimated using one-dimensional shear wave analysis considering the depth of engineering bedrock are different from those obtained considering top 30-m soil layers.

The nature of the charge-ordered state in Y0.5Ca0.5MnO3 with a very small average radius of the A-site cations

A detailed investigation of Y0.5Ca0.5MnO3 with a very small radius of the A-site cations ([r(A)] approximate to 1.13 Angstrom reveals the occurrence of a charge-ordering transition in the paramagnetic state, at a relatively high temperature of 260 K. The orthorhombic lattice distortion, as measured by the dimensionless index D, is large (similar to 1.75%) over the entire 300-100 K range, but the antiferromagnetic interactions become prominent only at low temperatures (< 160 K). The charge-ordering gap in Y0.5Ca0.5MnO3, measured by low-temperature vacuum tunnelling spectroscopy, is large (similar to 0.5 eV) and the charge-ordered state is unaffected by the application of a magnetic field of 6 T. The study indicates that the nature of charge-ordering in Y0.5Ca0.5MnO3 which is dominated by the cooperative Jahn-Teller effect and the associated lattice distortion is distinctly different from analogous manganates with larger [r(A)].

The role of lysine-41 in RNase A catalysis - A quantum chemical study on the active site ligand complex

Several mechanisms have been proposed to explain the action of enzymes at the atomic level. Among them, the recent proposals involving short hydrogen bonds as a step in catalysis by Gerlt and Gassman [1] and proton transfer through low barrier hydrogen bonds (LBHBs) [2, 3] have attracted attention. There are several limitations to experimentally testing such hypotheses, Recent developments in computational methods facilitate the study of active site-ligand complexes to high levels of accuracy, Our previous studies, which involved the docking of the dinucleotide substrate UpA to the active site of RNase A [4, 5], enabled us to obtain a realistic model of the ligand-bound active site of RNase A. From these studies, based on empirical potential functions, we were able to obtain the molecular dynamics averaged coordinates of RNase A, bound to the ligand UpA. A quantum mechanical study is required to investigate the catalytic process which involves the cleavage and formation of covalent bonds. In the present study, we have investigated the strengths of some of the hydrogen bonds between the active site residues of RNase A and UpA at the ab initio quantum chemical level using the molecular dynamics averaged coordinates as the starting point. The 49 atom system and other model systems were optimized at the 3-21G level and the energies of the optimized systems were obtained at the 6-31G* level. The results clearly indicate the strengthening of hydrogen bonds between neutral residues due to the presence of charged species at appropriate positions. Such a strengthening manifests itself in the form of short hydrogen bonds and a low barrier for proton transfer. In the present study, the proton transfer between the 2'-OH of ribose (from the substrate) and the imidazole group from the H12 of RNase A is influenced by K41, which plays a crucial role in strengthening the neutral hydrogen bond, reducing the barrier for proton transfer.

Mycobacterium tuberculosis pantothenate kinase: possible changes in location of ligands during enzyme action

The crystal structures of complexes of Mycobacterium tuberculosis pantothenate kinase with the following ligands have been determined: (i) citrate; (ii) the nonhydrolysable ATP analogue AMPPCP and pantothenate (the initiation complex); (iii) ADP and phosphopantothenate resulting from phosphorylation of pantothenate by ATP in the crystal (the end complex); (iv) ATP and ADP, each with half occupancy, resulting from a quick soak of crystals in ATP (the intermediate complex); (v) CoA; (vi) ADP prepared by soaking and cocrystallization, which turned out to have identical structures, and (vii) ADP and pantothenate. Solution studies on CoA binding and catalytic activity have also been carried out. Unlike in the case of the homologous Escherichia coli enzyme, AMPPCP and ADP occupy different, though overlapping, locations in the respective complexes; the same is true of pantothenate in the initiation complex and phosphopantothenate in the end complex. The binding site of MtPanK is substantially preformed, while that of EcPanK exhibits considerabl plasticity. The difference in the behaviour of the E. coli and M. tuberculosis enzymes could be explained in terms of changes in local structure resulting from substitutions. It is unusual for two homologous enzymes to exhibit such striking differences in action. Therefore, the results have to be treated with caution. However, the changes in the locations of ligands exhibited by M. tuberculosis pantothenate kinase are remarkable and novel.

A linear programming approach for estimating the structure of a sparse linear genetic network from transcript profiling data

Background: A genetic network can be represented as a directed graph in which a node corresponds to a gene and a directed edge specifies the direction of influence of one gene on another. The reconstruction of such networks from transcript profiling data remains an important yet challenging endeavor. A transcript profile specifies the abundances of many genes in a biological sample of interest. Prevailing strategies for learning the structure of a genetic network from high-dimensional transcript profiling data assume sparsity and linearity. Many methods consider relatively small directed graphs, inferring graphs with up to a few hundred nodes. This work examines large undirected graphs representations of genetic networks, graphs with many thousands of nodes where an undirected edge between two nodes does not indicate the direction of influence, and the problem of estimating the structure of such a sparse linear genetic network (SLGN) from transcript profiling data. Results: The structure learning task is cast as a sparse linear regression problem which is then posed as a LASSO (l1-constrained fitting) problem and solved finally by formulating a Linear Program (LP). A bound on the Generalization Error of this approach is given in terms of the Leave-One-Out Error. The accuracy and utility of LP-SLGNs is assessed quantitatively and qualitatively using simulated and real data. The Dialogue for Reverse Engineering Assessments and Methods (DREAM) initiative provides gold standard data sets and evaluation metrics that enable and facilitate the comparison of algorithms for deducing the structure of networks. The structures of LP-SLGNs estimated from the INSILICO1, INSILICO2 and INSILICO3 simulated DREAM2 data sets are comparable to those proposed by the first and/or second ranked teams in the DREAM2 competition. The structures of LP-SLGNs estimated from two published Saccharomyces cerevisae cell cycle transcript profiling data sets capture known regulatory associations. In each S. cerevisiae LP-SLGN, the number of nodes with a particular degree follows an approximate power law suggesting that its degree distributions is similar to that observed in real-world networks. Inspection of these LP-SLGNs suggests biological hypotheses amenable to experimental verification. Conclusion: A statistically robust and computationally efficient LP-based method for estimating the topology of a large sparse undirected graph from high-dimensional data yields representations of genetic networks that are biologically plausible and useful abstractions of the structures of real genetic networks. Analysis of the statistical and topological properties of learned LP-SLGNs may have practical value; for example, genes with high random walk betweenness, a measure of the centrality of a node in a graph, are good candidates for intervention studies and hence integrated computational – experimental investigations designed to infer more realistic and sophisticated probabilistic directed graphical model representations of genetic networks. The LP-based solutions of the sparse linear regression problem described here may provide a method for learning the structure of transcription factor networks from transcript profiling and transcription factor binding motif data.

Competing A-site and B-site driven ferroelectric instabilities in the (1-x)PbTiO3-(x)BiAlO3 system

The system (1-x)PbTiO3-(x)BiAlO3 has been investigated with regard to its solid solubility, crystal structure, microstructure, and ferroelectric transition. The unit cell volume and the tetragonality exhibit anomalous behavior near x=0.10. The Curie point (T-C) of PbTiO3 was however found to be nearly unchanged. The study seems to suggest that the decrease in the stability of the ferroelectric state due to dilution of the Ti-sublattice by smaller sized Al+3 ions is compensated by the increase in the ferroelectric stability by the Bi+3 ions.

Site classification and estimation of surface level seismic hazard using geophysical data and probabilistic approach

This paper presents the site classification of Bangalore Mahanagar Palike (BMP) area using geophysical data and the evaluation of spectral acceleration at ground level using probabilistic approach. Site classification has been carried out using experimental data from the shallow geophysical method of Multichannel Analysis of Surface wave (MASW). One-dimensional (1-D) MASW survey has been carried out at 58 locations and respective velocity profiles are obtained. The average shear wave velocity for 30 m depth (Vs(30)) has been calculated and is used for the site classification of the BMP area as per NEHRP (National Earthquake Hazards Reduction Program). Based on the Vs(30) values major part of the BMP area can be classified as ``site class D'', and ``site class C'. A smaller portion of the study area, in and around Lalbagh Park, is classified as ``site class B''. Further, probabilistic seismic hazard analysis has been carried out to map the seismic hazard in terms spectral acceleration (S-a) at rock and the ground level considering the site classes and six seismogenic sources identified. The mean annual rate of exceedance and cumulative probability hazard curve for S. have been generated. The quantified hazard values in terms of spectral acceleration for short period and long period are mapped for rock, site class C and D with 10% probability of exceedance in 50 years on a grid size of 0.5 km. In addition to this, the Uniform Hazard Response Spectrum (UHRS) at surface level has been developed for the 5% damping and 10% probability of exceedance in 50 years for rock, site class C and D These spectral acceleration and uniform hazard spectrums can be used to assess the design force for important structures and also to develop the design spectrum.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.