Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.

Tertiary structure of an amyloid immunoglobulin light chain protein: a proposed model for amyloid fibril formation.

An immunoglobulin light chain protein was isolated from the urine of an individual (BRE) with systemic amyloidosis. Complete amino acid sequence of the variable region of the light chain (VL) protein established it as a kappa I, which when compared with other kappa I amyloid associated proteins had unique residues, including Ile-34, Leu-40, and Tyr-71. To study the tertiary structure, BRE VL was expressed in Escherichia coli by using a PCR product amplified from the patient BRE's bone marrow DNA. The PCR product was ligated into pCZ11, a thermal-inducible replication vector. Recombinant BRE VL was isolated, purified to homogeneity, and crystallized by using ammonium sulfate as the precipitant. Two crystal forms were obtained. In crystal form I the BRE VL kappa domain crystallizes as a dimer with unit cell constants isomorphous to previously published kappa protein structures. Comparison with a nonamyloid VL kappa domain from patient REI, identified significant differences in position of residues in the hypervariable segments plus variations in framework region (FR) segments 40-46 (FR2) and 66-67 (FR3). In addition, positional differences can be seen along the two types of local diads, corresponding to the monomer-monomer and dimer-dimer interfaces. From the packing diagram, a model for the amyloid light chain (AL) fibril is proposed based on a pseudohexagonal spiral structure with a rise of approximately the width of two dimers per 360 degree turn. This spiral structure could be consistent with the dimensions of amyloid fibrils as determined by electron microscopy.

Cell Surface Assembly of HIV gp41 Six-Helix Bundles for Facile, Quantitative Measurements of Hetero-oligomeric Interactions

Helix helix interactions are fundamental to many biological signals and systems and are found in homo- or heteromultimerization of signaling molecules as well as in the process of virus entry into the host. In HIV, virus-host membrane fusion during infection is mediated by the formation of six-helix bundles (6HBs) from homotrimers of gp41, from which a number of synthetic peptides have been derived as antagonists of virus entry. Using a yeast surface two-hybrid (YS2H) system, a platform designed to detect protein-protein interactions occurring through a secretory pathway, we reconstituted 6HB complexes on the yeast surface, quantitatively measured the equilibrium and kinetic constants of soluble 6HB, and delineated the residues influencing homo-oligomeric and hetero-oligomeric coiled-coil interactions. Hence, we present YS2H as a platform for the facile characterization and design of antagonistic peptides for inhibition of HIV and many other enveloped viruses relying on membrane fusion for infection, as well as cellular signaling events triggered by hetero-oligomeric coiled coils.

Cell Dynamics of Model Proteins

We design rapidly folding sequences by assigning the strongest couplings to the contacts present in a target native state in a two dimensional model of heteropolymers. The pathways to folding and their dependence on the temperature are illustrated via a mapping of the dynamics into motion within the space of the maximally compact cells.

HNbWO6 and HTaWO6: Novel oxides related to ReO3 formed by ion exchange of rutile-type LiNbWO6 and LiTaWO6

Both LiNbWO6 and LiTaWO6 undergo ion exchange in hot aqueous H2SO4 yielding the hydrates HMWO6 · H2O (M = Nb or Ta). The reaction is accompanied by a structural transformation from the rutile to the ReO3 structure. The cell constants are a = 3.783(3)Å for HNbWO6 · H2O and a = 3.785(5)Å for HTaWO6 · H2O. The ReO3 structure is retained by the dehydration products HMWO6 and MWO5.5 as well. HMWO6 phases yield H1+xMWO6 hydrogen bronzes on exposure to hydrogen in the presence of platinum catalyst.

HNbWO6 and HTaWO6: Novel layered oxides related to the rutile structure. Synthesis and investigation of ion-exchange and intercalation behaviour

New protonated layered oxides, HMWO6·1.5H2O (M=Nb or Ta), have been synthesized by topotactic exchange of lithium in trirutile LiMWO6 with protons by treatment with dilute HNO3. The tetragonal cell constants are a=4.71 (2) and c=25.70 (8)Å for HNbWO6·1.5H2O and a=4.70 (2) and c=25.75 (9) Å for HTaWO6·1.5H2O. Partially hydrated compounds, HMWO6·0.5H2O and anhydrous compounds, HMWO6 retain the layered structure. The structure of these oxides consists of MWO6 sheets built up of M/W-oxygen octahedra with rutile type corner- and edge-sharing. Interlayer protons in HMWO6 are exchanged with Li+, Na+, K+ and Tl+. HMWO6 exhibit Brønsted acidity intercalating n-alkylamines and pyridine.

Analysis of reflection characteristics of a normal incidence plane wave on resonant sound absorbers: A finite element approach

Resonant sound absorbers are used widely as anechoic coatings in underwater applications. In this paper a finite element scheme based on the Galerkin technique is used to analyze the reflection characteristics of the resonant absorber when insonified by a normal incidence plane wave. A waveguide theory coupled with an impedance matching condition in the fluid is used to model the problem. It is shown in this paper that the fluid medium encompassing the absorber can be modeled as an elastic medium with equivalent Lamé constants. Quarter symmetry conditions within the periodic unit cell are exploited. The finite element results are compared with analytical results, and with results published elsewhere in the literature. It is shown in the process that meshing of the fluid domain can be obviated if the transmission coefficients or reflection coefficients only are desired as is often the case. Finally, some design curves for thin resonant absorbers with water closure are presented in this paper.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Dielectric properties of (110) oriented PbZrO3 and La-modified PbZrO3 thin films grown by sol-gel process on Pt(111)/Ti/SiO2/Si substrate

Highly (110) preferred orientated antiferroelectric PbZrO3 (PZ) and La-modified PZ thin films have been fabricated on Pt/Ti/SiO2/Si substrates using sol-gel process. Dielectric properties, electric field induced ferroelectric polarization, and the temperature dependence of the dielectric response have been explored as a function of composition. The Tc has been observed to decrease by ∼ 17 °C per 1 mol % of La doping. Double hysteresis loops were seen with zero remnant polarization and with coercive fields in between 176 and 193 kV/cm at 80 °C for antiferroelectric to ferroelectric phase transformation. These slim loops have been explained by the high orientation of the films along the polar direction of the antiparallel dipoles of a tetragonal primitive cell and by the strong electrostatic interaction between La ions and oxygen ions in an ABO3 perovskite unit cell. High quality films exhibited very low loss factor less than 0.015 at room temperature and pure PZ; 1 and 2 mol % La doped PZs have shown the room temperature dielectric constant of 135, 219, and 142 at the frequency of 10 kHz. The passive layer effects in these films have been explained by Curie constants and Curie temperatures. The ac conductivity and the corresponding Arrhenius plots have been shown and explained in terms of doping effect and electrode resistance.

Magnetic and dielectric interactions in nano zinc ferrite powder: Prepared by self-sustainable propellant chemistry technique

The structural, magnetic and dielectric properties of nano zinc ferrite prepared by the propellant chemistry technique are studied. The PXRD measurement at room temperature reveal that the compound is in cubic spinel phase, belong to the space group Fd (3) over barm. The unit cell parameters have been estimated from Rietveld refinement. The calculated force constants from FTIR spectrum corresponding to octahedral and tetrahedral sites at 375 and 542 cm(-1) are 6.61 x 10(2) and 3.77 x 10(2) N m(-1) respectively; these values are slightly higher compared to the other ferrite systems. Magnetic hysteresis and EPR spectra show superparamagnetic property nearly to room temperature due to comparison values between magnetic anisotropy energy and the thermal energy. The calculated values of saturation magnetization, remenant magnetization, coercive field and magnetic moment supports for the existence of multi domain particles in the sample. The temperature dependent magnetic field shows the spin freezing state at 30 K and the blocking temperature at above room temperature. The frequency dependent dielectric interactions show the variation of dielectric constant, dielectric loss and impedance as similar to other ferrite systems. The AC conductivity in the prepared sample is due to the presence of electrons, holes and polarons. The synthesized material is suitable for nano-electronics and biomedical applications. (C) 2014 Elsevier B.V. All rights reserved.

Pressure and thermal effects on elastic properties of single crystal alpha-Al2O3 from Monte-Carlo simulation

A rectangular structural unit cell of a-Al2O3 is generated from its hexagonal one. For the rectangular structural crystal with a simple interatomic potential [Matsui, Mineral Mag. 58A, 571 (1994)], the relations of lattice constants to homogeneous pressure and temperature are calculated by using Monte-Carlo method at temperature 298K and 0 GPa, respectively. Both numerical results agree with experimental ones fairly well. By comparing pair distribution function, the crystal structure of a-Al2O3 has no phase transition in the range of systematic parameters. Based on the potential model, pressure dependence of isothermal bulk moduli is predicted. Under variation of general strains, which include of external and internal strains, elastic constants of a-Al2O3 in the different homogeneous load are determined. Along with increase of pressure, axial elastic constants increase appreciably, but nonaxial elastic constants are slowly changed.

Crystallographic and magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.

Hydrogenation and anisotropic expansions in R3Fe29-xTx (R = Y, Ce, Nd, Sm, Gd, Tb and Dy; T = V and Cr)

A systematic study of the phase formation, structure and magnetic properties of the R3Fe29-xTx compounds (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) has been performed upon hydrogenation. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions mainly along the a- and b-axis rather than along the c-axis are observed for all of the compounds upon hydrogenation. Hydrogenation leads to an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. First order magnetization processes (FOMP) occur in the external magnetic fields for Nd3Fe24.5Cr4.5H5.0, Tb3Fe27.0Cr2.0H2.8, and Gd3Fe28.0Cr1.0H4.2 compounds.

Structural and magnetic properties of hydrides R3Fe29-xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R3Fe29 - xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants a, b, and c and the unit cell volume of R3Fe29 - xVxHy decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce3Fe27.5V1.5H6.5, like Ce3Fe27.5V1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce3Fe27.5V1.5 and Gd3Fe28.4V0.6 show the larger storage of hydrogen with y = 6.5 and 6.9 in these hydrides. (C) 1998 Elsevier Science B.V. All rights reserved.

Crystallographic and magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic study of the structural and intrinsic magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Hydrogenation lends to a relative volume expansion of the unit cell and a decrease in x-ray density for each compound. Anisotropic expansions mainly along the n- and b-axes rather than along the c-axis for all of the compounds upon hydrogenation are observed. The lattice constants and the unit-cell volume of R3Fe29-xCrx and R3Fe29-xCrxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. After hydrogenation a decrease of 0.34 mu(B)/Fe in the average Fe atomic magnetic moment and a slight increase in the anisotropy field for Y3Fe27.2Cr1.8 are achieved at 4.2 K. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and TD3Fe27.0Cr2.0H2.8, and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2. The abnormal crystallographic and magnetic properties of Ce3Fe25.0Cr4.0 and Ce3Fe25.0Cr4.0H5.4 suggest that the Ce ion non-triply ionized.