Structural phase transitions in Bi2V1-xGexO5.5-x/2 (x=0.2, 0.4, and 0.6) single crystals: X-ray crystallographic study

Single crystals of Bi2V1-xGexO5.5-x/2 (x = 0.2, 0.4, and 0.6) were grown by slow cooling of melts. Bismuth vanadate transforms from an orthorhombic to a tetragonal structure and subsequently to an orthorhombic system when the Ge4+ concentration was varied from x = 0.2 to x = 0.6. All of these compositions crystallized in polar space groups (Aba2, F4mm, and Fmm2 for x = 0.2, 0.4, and 0.6, respectively). The structures were fully determined by single crystal X-ray diffraction studies, (C) 1999 Elsevier Science Ltd.

Stress-strain Curves and Corresponding Structural Parameters in Mulberry and Non-mulberry Silk Fibers

Mulberry fiber (Bivoltine) and non-mulberry fiber (Tassar) were subjected to stress-strain studies and the corresponding samples were examined using wide angle X-ray scattering studies. Here we have two different characteristic stress-strain curves and this has been correlated with changes in crystallite shape ellipsoids in all the fibers. Exclusive crystal structure studies of Tassar fibers show interesting feature of transformation from antiparallel chains to parallel chains.

The studies on micro-structural defects in deformed composite matrix of Al-Si-Mg and SiC

Detailed Fourier line shape analysis has been performed on three different compositions of the composite matrix of Al-Si-Mg and SiC. The alloy composition in wt% is Al-7%Si, 0.35%Mg, 0.14%Fe and traces of copper and titanium (similar to 0.01%) with SiC varying from 0 to 30wt% in three steps i.e., 0, 10 and 30wt%. The line shift analysis has been performed by considering 111, 200, 220, 311 and 222 reflections after estimating their relative shift. Peak asymmetry analysis has been performed considering neighbouring 111 and 200 reflections and Fourier line shape analysis has been performed after considering the multiple orders 111 and 222, 200 and 400 reflections. Combining all these three analyses it has been found that the deformation stacking faults both intrinsic alpha' and extrinsic alpha " are absent in this alloy system whereas the deformation twin beta has been found to be positive and increases with the increase of SiC concentration. So, like other Al-base alloys this ternary alloy also shows high stacking fault energy, and the addition of SiC introduces deformation twin which increases with its concentration in the deformed lattices.

Conformation and orientation of alkyl chains in the layered organic-inorganic hybrids: (CnH2n+1NH3)(2)PbI4 (n=12,16,18)

Layered organic inorganic hybrids based on perovskite-derived alkylammonium lead halides have been demonstrated as important new materials in the construction of molecular electronic devices. Typical of this class of materials are the single-perovskite slab lead iodides of the general formula (CnH2n+1NH3)(2)PbI4. While for small n, these compounds are amenable to single-crystal structure determination, the increasing degree of disorder in the long chain (n = 12,14...) compounds makes such an analysis difficult. In this study, we use powder X-ray diffraction, and vibrational and C-13 NMR spectroscopies to establish the conformation, orientation and organization of hydrocarbon chains in the series of layered alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4 (n = 12,16,18). We find that the alkyl chains adopt a tilted bilayer arrangement, while the structure of the inorganic layer remains invariant with respect to the value of n. Conformation-sensitive methylene stretching modes in the infrared and Raman spectra, as well as the C-13 NMR spectra indicate that bonds in the methylene chain are in trans configuration. The skeletal modes of the alkyl chain in the Raman spectra establish that there is a high degree of all-trans conformational registry for the values of n studied here. From the orientation dependence of the infrared spectra of crystals of (CnH2n+1NH3)(2)PbI4 ( n = 12,16), we find that the molecular axis of the all-trans alkyl chains are tilted away from the interlayer normal by an angle of 55degrees. This value of this tilt angle is consistent with the dependence of the c lattice expansion as a function of n, as determined from powder X-ray diffraction.

Electron diffraction structure analysis: structural research with low-quality diffraction data

Electron Diffraction Structure Analysis (EDSA) with data from standard selected-area electron diffraction (SAED) is still the method of choice for structure determination of nano-sized single crystals. The recently determined heavy atom structure α-Ti2Se (Albe & Weirich, 2003) is used as an example to illustrate the developed procedure for structure determination from two-dimensionally SAED data via direct methods and kinematical least-squares refinement. Despite the investigated crystallite had a relatively large effective thickness of about 230 Å as determined from dynamical calculations, the obtained structural model from SAED data was found in good agreement with the result from an earlier single crystal X-ray study (Weirich, Pöttgen & Simon, 1996). Arguments, which support the validity of the used quasi-kinematical approach, are given in the text. The influences of dynamical and secondary scattering on the quality of the data and the structure solution are discussed. Moreover, the usefulness of first-principles calculations for verifying the results from EDSA is demonstrated by two examples, whereas one of the structures was unattainable by conventional X-ray diffraction.

Design and structural analysis of hairpin-TFO for transcriptional activation of genes in S-cerevisiae

Triplex forming oligonucleotides (TFOs) have the potential to modulate gene expression. While most of the experiments are directed towards triplex mediated inhibition of gene expression the strategy potentially could be used for gene specific activation. In an attempt to design a strategy for gene specific activation in vivo applicable to a large number of genes we have designed a TFO based activator-target system which may be utilized in Saccharomyces cerevisiae or any other system where Gal4 protein is ectopically expressed. The total genome sequence of Saccharomyces cerevisiae and expression profiles were used to select the target genes with upstream poly (pu/py) sequences. We have utilized the paradigm of Gal4 protein and its binding site. We describe here the selection of target genes and design of hairpin-TFO including the targeting sequences containing polypurine stretch found in the upstream promoter regions of weakly expressed genes. We demonstrate, the formation of hairpin-TFO, its binding to Gal4 protein, its ability to form triplex with the target duplex in vitro, the effect of polyethylenimine on complex formation and discuss the implication on in vivo transcription activation.

Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation

The diphosphazane ligands of the type, (C20H12O2)PN(R)P(E)Y2 (R = CHMe2 or (S)-*CHMePh; E = lone pair or S; Y2 = O2C20H12 or Y = OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl2{ηsu2}-((O2C20H12)PN((S)-*CHMePh)PPh2] has been determined by X-ray crystallography. The reactions of [CpRu(PPh3)2Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X2PN(R)PYY′ (R = CHMe2 or (S)-*CHMePh; X = C6H5 or X2 = O2C20H12; Y=Y′= C6H5 or Y = C6H5, Y′ = OC6H4Me-4 or OC6H3Me2-3,5 or N2C3HMe2-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη2-Ph2PN((S)-*CHMePh)*PPh (N2C3HMe2-3,5)Cl] is established by X-ray diffraction. The reactions of Ru3(CO)12 with the diphosphazanes (C20H12O2)PN(R)PY2 (R = CHMe2orMe; Y2=O2C20H12or Y= OC6H5 or OC6H4Me-4 or OC6H4OMe-4 or OC6H4But-4 or C6H5) yield the triruthenium clusters [Ru3(CO)10{η-(O2C20H12)PN(R)PY2}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η3-allyl palladium complexes, [Pd(η3-l,3-R′2-C3H3){η2-(rac)-(02C20H12)PN(CHMe2)PY2}](PF6) (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.

Orthometalation in calixarenes: Synthesis and structural characterization of a novel orthopalladated calix[4]arene bisphosphite

The treatment of a symmetrically bridged p-Bu-t-calix[4] arene bisphosphite with PdCl2(NCPh)(2) yields a novel orthopalladated derivative by a C-C bond scission of a t-butyl group attached to an aryl ring. The structure of this orthopalladated calix[4]arene derivative has been established by X-ray crystallography.

Solid state structural and solution studies on the formation of a flexible cavity for anions by copper(I) and 1,2-bis(diphenylphosphino)ethane

Copper(l) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu-2(dppe)(3)(X)(2) [X- = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu-2(dPPe)(3)](2+) dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1 -3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior. (C) 2002 Elsevier Science Ltd. All rights reserved.

Structural and dielectric studies on poly(l-lithocholic acid)

In this paper, we report the results pretaining to the study of the structural, microstructural and the dielectric properties of poly(I-lithocholic acid) (PL), and the composite of PL dispersed in PMMA. The density of the composites was measured using Archimedes principle. The microstructural properties of the composities were studied using XRD and SEM techniques, which give an idea about the dispersion of the polymer PL in the PMMA matrix. The dielectric constants er of the composites were measured with a HP 4194A Impedance/Gain-Phase Analyzer in the frequency range 100 Hz-40 MHz at room temperature. The dielectric constants of the composites at different frequencies were predicted using Clasius-Mossotti and Maxwell's models.

Structural basis for poor uracil excision from hairpin DNA

Two-dimensional NMR and molecular dynamics simulations have been used to determine the three-dimensional structures of two hairpin DNA structures: d-CTAGAG GATCCUTTTGGATCCT (abbreviated as U1-hairpin) and d-CTAGAGGATCCTTUTGGATCCT (abbreviated as U3-hairpin). The (1) H resonances of both of these hairpin structures have been assigned almost completely. NMR restrained molecular dynamics and energy minimization procedures have been used to describe the three-dimensional structures of these hairpins. This study and concurrent NMR structural studies on two other d-CTAGAGGA TCCTUTTGGATCCT (abbreviated as U2-hairpin) and d-CTAGAGGATCCTTTUGGATCCT (abbreviated as U4-hairpin) have shed light upon various interactions reported between Echerichia coli uracil DNA glycosylase (UDG) and uracil-containing DNA. The backbone torsion angles, which partially influence the local conformation of U12 and U14 in U1 and U3-hairpins, respectively, are probably locked in the trans conformation as in the case of U-13 in the U2-hairpin. Such a stretched-out backbone conformation in the vicinity of U-12 and U-14 is thought to be the reason why the K-m value is poor for U1- and U3-hairpins as it is for the U2-hairpin. Furthermore, the bases U-12 and U-14 in both U1- and U3-hairpins adopt an anti conformation, in contrast with the base conformation of U-13 in the U2-hairpin, which adopts a syn conformation. The clear discrepancy observed in the U-base orientation with respect to the sugar moieties could explain why the V-max value is 10- to 20-fold higher for the U1- and U3-hairpins compared with the U2-hairpin. Taken together, these observations support our interpretation that the unfavourable backbone results in a poor K-m value, whereas the unfavourable nucleotide conformation results in a poor V-max value. These two parameters therefore make the U1- and U3-hairpins better substrates for UDG compared with the U2-hairpin, as reported earlier [Kumar, N. V. & Varshney, U. (1997) Nucleic Acids Res. 25, 2336-2343.].

Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-delta solid solution

The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended X-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-delta (x = 0.03 and 0.05; delta similar to 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % Cu/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Angstrom, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+ - at 2.92 Angstrom and -Cu2+-O2--Ce4+- at the distance of 3.15 Angstrom, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-delta type of solid solution phase having -square-Cu2+-O-Ce4+- kind of linkages.

Structural model for the Cu-B site of dopamine beta-hydroxylase: Crystal structure of a copper(II) complex showing N3OS coordination with an axial sulfur ligation

A copper(II) complex containing a NSO-donor Schiff base and NN-donor 2,2'-bipyridine has been prepared and structurally characterized. The square pyramidal complex with an axial sulfur ligation is a structural model for the CUB site of dopamine-hydroxylase in its oxidized form. The copper(II) complex is catalytically active in the oxidation of ascorbic acid by dioxygen mediated by a copper(I) species which is proposed to have a four-coordinate structure with a N3S coordination geometry.

Structural vibration control using resistively shunted piezoceramics

Application of piezoceramic materials in actuation and sensing of vibration is of current interest. Potential and more popular applications of piezoceramics are probably in the field of active vibration control. However, the objective of this work is to investigate the effect of shunted piezoceramics as passive vibration control devices when bonded to a host structure. Resistive shunting of a piezoceramic bonded to a cantilevered duralumin beam has been investigated. The piezoceramic is connected in parallel to an electrical network comprising of resistors and inductors. The piezoceramic is a capacitor that stores and discharges electrical energy that is transformed from the mechanical motion of the structure to which it is bonded. A resistor across the piezoceramic would be termed as a resistively shunted piezoceramic. Similarly, an inductor across the piezoceramic is termed as a resonantly shunted piezoceramic. In this study, the effect of resistive shunting on the nature of damping enhancement to the host structure has been investigated. Analytical studies are presented along with experimental results.

Systematic trends in structural and thermodynamic properties of ternary oxides in the systems Ln-Pd-O (Ln = lanthanide element)

Isothermal sections of the phase diagrams for the systems Ln-Pd-O (Ln = lanthanide element) at 1223 K indicate the presence of two inter-oxide compounds Ln(4)PdO(7) and Ln(2)Pd(2)O(5) for Ln = La, Pr, Nd, Sm, three compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) for Ln = Eu, Gd and only one compound of Ln(2)Pd(2)O(5) for Ln = Tb to Ho. The lattice parameters of the compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) show systematic nonlinear variation with atomic number. The unit cell volumes decrease with increasing atomic number. The standard Gibbs energies, enthalpies and entropies of formation of the ternary oxides from their component binary oxides (Ln(2)O(3) and PdO) have been measured recently using an advanced version of the solid-state electrochemical cell. The Gibbs energies and enthalpies of formation become less negative with increasing atomic number of Ln. For all the three compounds, the variation in Gibbs energy and enthalpy of formation with atomic number is markedly non-linear. The decrease in stability with atomic number is most pronounced for Ln(2)Pd(2)O(5), followed by Ln(4)PdO(7) and Ln(2)PdO(4). This is probably related to the repulsion between Pd2+ ions on the opposite phases Of O-8 cubes in Ln(2)Pd(2)O(5), and the presence of Ln-filled O-8 cubes that share three faces with each other in Ln4PdO7. The values for entropy of formation of all the ternary oxides from their component binary oxides are relatively small. Although the entropies of formation show some scatter, the average value for Ln = La, Pr, Nd is more negative than the average value for the other lanthanide elements. From this difference, an average value for the structure transformation entropy of Ln(2)O(3) from C-type to A-type is estimated as 0.87 J.mol(-1).K-1. The standard Gibbs energies of formation of these ternary oxides from elements at 1223 K are presented as a function of lanthanide atomic number. By invoking the Neumann-Kopp rule for heat capacity, thermodynamic properties of the inter-oxide compounds at 298.15 K are estimated. (C) 2002 Elsevier Science Ltd. All rights reserved.