Beta-structure of polypeptides in non-aqueous solutions. I. Spectral characteristics of the polypeptide backbone

The optical rotatory features of the beta-structure of the polypeptides in non-aqueous solutions and films cast from these solutions have been investigated. The beta-structure of poly-S-benzyl-L-cysteine, poly-S-carbobenzoxy-L-cysteine and poly-S-benzyl-L-cysteine, poly-S-carbobenzoxy-L-cysteine and poly-O-carbo-bands of their films. The optical rotatory dispersion (ORD) and circular dichroism (CD) spectra of these polypeptides are found to be very similar in both film and solution. In solvents promoting the beta-structure, the polypeptides are characterized by CD troughs in the n-pi* transition region of the peptide chromophore. The ORD spectra are found to be positive in sign throughout the visible and accessible ultraviolet regions and are interpreted in terms of the possible existence of a relatively much larger positive pi-pi* CD bands as compared with the negative n-pi* band. The rotatory data obtained in the non-aqueous solution are compared with those obtained for other poly peptides in aqueous solutions, with respect to the type and extent of beta-structure present.

Including the fermion vacuum fluctuations in the (2+1) flavor Polyakov quark-meson model

We consider the (2 + 1) flavor Polyakov quark-meson model and study the effect of including fermion vacuum fluctuations on the thermodynamics and phase diagram. The resulting model predictions are compared to the recent QCD lattice simulations by the HotQCD and Wuppertal-Budapest collaborations. The variation of the thermodynamic quantities across the phase transition region becomes smoother. This results in better agreement with the lattice data. Depending on the value of the mass of the sigma meson, including the vacuum term results in either pushing the critical end point into higher values of the chemical potential or excluding the possibility of a critical end point altogether.

Evolution of microstructure and texture in friction stir processed Al-Mg-Mn alloy

Friction stir processing was carried out on the Al-Mg-Mn alloy to achieve ultrafine grained microstructure. The evolution of microstructure and micro-texture was studied in different regions of the deformed sample, namely nugget zone, thermo-mechanically affected zone (TMAZ) and base metal. The average grain sizes of the nugget zone, TMAZ and base metal are 1.5 mu m +/- 0.5 mu m, 15 mu m +/- 8 mu m, and 80 mu m +/- 10 mu m, respectively. The TMAZ exhibits excessive deformation banding structure and sub-grain formation. The orientation gradient within the sub-grain is dependent on grain size, orientation, and distance from nugget zone. The microstructure was partitioned based on the grain orientation spread and grain size values to separate the recrystallized fraction from the deformed region in order to understand the micromechanism of grain refinement. The texture of both deformed and recrystallized regions are similar in nature. Microstructure and texture analysis suggest that the restoration processes are different in different regions of the processed sample. The transition region between nugget zone and TMAZ exhibits large elongated grains surrounded by fine equiaxed grains of different orientation which indicate the process of discontinuous dynamic recrystallization. Within the nugget zone, similar texture between deformed and recrystallized grain fraction suggests that the restoration mechanism is a continuous process.

Reduced graphene oxide induced phase miscibility in polystyrene-poly(vinyl methyl ether) blends

Graphene oxide and reduced graphene oxide (r-GO) were synthesized by wet chemistry and the effect of r-GO in PS-PVME blends was investigated here with respect to phase miscibility, intermolecular cooperativity in the glass transition region and concentration fluctuation variance by shear rheology and dielectric spectroscopy. The spinodal decomposition temperature (T-s) and correlation length were evaluated from isochronal temperature scans in shear rheology. The r-GO is shown to induce miscibility in the blends, which may lead to increased local heterogeneity in the blends, though the length of cooperatively re-arranged regions (xi) at T-g is more or less unaltered. The evolution of the phase morphology as a function of temperature was assessed using polarized optical microscopy (POM). In the case of the 60/40 PS-PVME blends with 0.25 wt% r-GO, apart from significant refinement in the morphology, retention of the interconnected ligaments of PVME was observed, even in the late stages of phase separation suggesting that the coarsening of the phase morphology has been slowed down in the presence of r-GO. This phenomenon was also supported by AFM. Surface enrichment of PVME, owing to its lower surface tension, in the demixed samples was supported by XPS scans. The interconnected network of PVME has resulted in significantly higher permittivity in the bi-phasic blends, although the concentration of r-GO is below the percolation threshold.

Phase-field elasticity model based on mechanical jump conditions

Computational models based on the phase-field method typically operate on a mesoscopic length scale and resolve structural changes of the material and furthermore provide valuable information about microstructure and mechanical property relations. An accurate calculation of the stresses and mechanical energy at the transition region is therefore indispensable. We derive a quantitative phase-field elasticity model based on force balance and Hadamard jump conditions at the interface. Comparing the simulated stress profiles calculated with Voigt/Taylor (Annalen der Physik 274(12):573, 1889), Reuss/Sachs (Z Angew Math Mech 9:49, 1929) and the proposed model with the theoretically predicted stress fields in a plate with a round inclusion under hydrostatic tension, we show the quantitative characteristics of the model. In order to validate the elastic contribution to the driving force for phase transition, we demonstrate the absence of excess energy, calculated by Durga et al. (Model Simul Mater Sci Eng 21(5):055018, 2013), in a one-dimensional equilibrium condition of serial and parallel material chains. To validate the driving force for systems with curved transition regions, we relate simulations to the Gibbs-Thompson equilibrium condition

Dynamical Transition of Water in the Grooves of DNA Duplex at Low Temperature

At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.

Magnetic susceptibility studies of lead oxyhalide glasses containing transition metal oxides

Magnetic susceptibility studies of lead oxyhalide glasses containing high concentrations of transition metal oxides such as MnO and Fe2O3 have been performed. While they exhibit predominantly antiferromagnetic interactions, the low temperature (<100K) region is dominated by paramagnetic contributions. The behaviour in these glasses is found to be similar to that of covalent oxide glasses and is different from that of purely ionic sulphate glasses.

The Influence of Bilayer Composition on the Gel to Liquid Crystalline Transition

We report molecular dynamics simulations of bilayers using a united atom model with explicit solvent molecules. The bilayer consists of the single tail cationic surfactant behenyl trimethyl ammonium chloride (BTMAC) with stearyl alcohol (SA) as the cosurfactant. We study the gel to liquid crystalline transitions in the bilayer by varying the amount of water at fixed BTMAC to SA ratio as well as by varying the BTMAC to SA ratio at fixed water content. The bilayer is found to exist in the tilted, Lβ′ phase at low temperatures, and for the compositions investigated in this study, the Lβ′ to Lα melting transition occurred in the temperature range 330−338 K. For the highest BTMAC to SA composition (2:3 molar ratio), a diffuse headgroup−water interface is observed at lower temperatures, and an increase in the d-spacing occurs prior to the melting transition. This pretransition swelling is accompanied by a sharpening in the water density variation across the headgroup region of the bilayer. Signatures of this swelling effect which can be observed in the alkane density distributions, area per headgroup, and membrane thickness are attributed to the hydrophobic effect. At a fixed bilayer composition, the transition temperature (>338 K) from the Lβ′ to Lα transition obtained for the high water content bilayer (80 wt %) is similar to that obtained with low water content (54.3 wt %), confirming that the melting transition at these water contents is dominated by chain melting.

Structural phase transition study of the morphotropic phase boundary compositions of Na0.5Bi0.5TiO3-PbTiO3

Neutron, synchrotron x-ray powder diffraction and dielectric studies have been performed for morphotropic phase boundary (MPB) compositions of the (1 - x )Na1/2Bi1/2TiO3-xPbTiO(3) system. At room temperature, the MPB compositions (0.10 < x <= 0.15) consist of a mixture of rhombohedral (space group R3c) and tetragonal ( space group P4mm) structures with the fraction of tetragonal phase increasing with increasing PbTiO3 content. On heating, while the rhombohedral phase just outside the MPB region, i.e. x = 0.10, transforms directly to a cubic phase, the rhombohedral phase of the MPB compositions transforms gradually to a tetragonal phase, until interrupted by a rhombohedral-cubic phase transition. The correspondence of the dielectric anomalies with the structural transitions of the different compositions has been examined and compared with earlier reports.

Effect of disorder on the exponent in the coherence region in high temperature superconductors

Effect of disorder on the electrical resistance near the superconducting transition temperature in the paracoherence region of high temperature YBa2CU3O7-delta (YBCO) thin film superconductor is reported. For this, c-axis oriented YBa2Cu3O7-delta thin films having superconducting transition width varying between 0.27 K and 6 K were deposited using laser ablation and high pressure oxygen sputtering techniques. Disorder in these films was further created by using 100 MeV oxygen and 200 MeV silver ions with varying fluences. It is observed that the critical exponent in the paracoherence region for films with high transition temperature and small transition width is in agreement with the theoretically predicted value (gamma = 1.33) and is not affected by disorder, while for films with lower transition temperature and larger transition width the value of exponent is much larger as compared to that theoretically predicted and it varies from sample to sample and usually changes with disorder induced by radiation. This difference in the behaviour of the exponent has been explained on the basis of differences in the strength of weak links and the transition between temperatures T. and T, is interpreted as a percolation like transition with disorder. (c) 2006 Elsevier B.V. All rights reserved.

Novel phase-transition behavior in an aqueous electrolyte solution

We have investigated the near-critical behavior of the susceptibility of a ternary liquid mixture of 3-methylpyridine. water, and sodium bromide as a function of the salt concentration. The susceptibility was determined from light-scattering measurements performed at a scattering angle of 90 degrees in the one-phase region near the locus of lower consolute points. A sharp crossover from asymptotic Ising behavior to mean-field behavior has been observed at concentrations ranging from 8 to 16.5 mass% NaBr. The range of asymptotic Ising behavior shrinks with increasing salt concentration and vanishes at a NaBr concentration of about 17 mass%. where complete mean-field-like behavior of the susceptibility is observed. A simultaneous pronounced increase in the background scattering at concentrations above 15 mass%, as well as a dip in the critical locus at 17 mass % NaBr, suggests that this phenomenon can be interpreted as mean-field tricritical behavior associated with the formation of a microheterogeneous phase due to clustering of the molecules and ions. An analogy with tri critical behavior observed in polymer solutions as well as the possibility of a charge-density-wave phase is also discussed. In addition, we, have observed a third soap-like phase an the liquid-liquid interface in several binary and ternary liquid mixtures.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Analysis of edge delaminations in laminates through combined use of quasi-three-dimensional, eight-noded, two-noded and transition elements

The use of appropriate finite elements in different regions of a stressed solid can be expected to be economical in computing its stress response. This concept is exploited here in studying stresses near free edges in laminated coupons. The well known free edge problem of [0/90], symmetric laminate is considered to illustrate the application of the concept. The laminate is modelled as a combination of three distinct regions. Quasi-three-dimensional eight-noded quadrilateral isoparametric elements (Q3D8) are used at and near the free edge of the laminate and two-noded line elements (Q3D2) are used in the region away from the free edge. A transition element (Q3DT) provides a smooth inter-phase zone between the two regions. Significant reduction in the problem size and hence in the computational time and cost have been achieved at almost no loss of accuracy.

Synchrotron Study of the Dynamical Effects in the LVV Auger Transitions in the First-Row Transition Elements

The intensity ratio between L2-M45M45 and L3-M45M45 spectral features for both Fe and Co indicates significant tranfer of intensity from L2- to L3-M45M45 region due to Coster-Kronig L2-M45M45 transition. The L2-L3M45 transition can be suppressed by turning the photon energy between the L2 and L3 thresholds; however, the L3-M45M45 spectral shapes for Fe and Co do not change very significantly even at these photom energies unlike the cases of Ni, Cu and Zn, thus establishing that the M45-hole decays predominantly before the L3-hole Auger decay in the early transition elements in contrast to the late ones.

Metal-insulator transition in perovskite oxides: Tunneling experiments

In this paper we have investigated the composition-driven metal-insulator (MI) transitions in two ABO3 classes of perovskite oxides (LaNixCo1-xO3 and NaxTayW1-yO3) in the composition range close to the critical region by using the tunneling technique. Two types of junctions (point-contact and planar) have been used for the investigation covering the temperature range 0.4 Kregion as the MI transition is approached. However, there is a fairly strong thermal-smearing effect near the zero-bias region for ?V?<10kBT/e. $G(V)� has been found to follow a power law of the type G(V)=G0(1+{?V?/V*}n) with V*=const and with n=0.5 for samples in the weak-localization region. However, as the critical region of the MI transition is approached G0?0 and n?1. We also find that for samples lying in the weak-localization region ?=eV* has a well-defined dependence on ?0, the zero-temperature conductivity. The observed behavior can be explained either as a manifestation of depletion of density of states at the Fermi level as the MI transition is approached or as a manifestation of strong inelastic scattering in the junction region.