Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7star, open: Dependence of Tc on hole concentration

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7 (y=0.0, 0.1, 0.25 and 0.5) , derived from the parent insulator TlYSr2Cu2O7, have been investigated for different values of x. XANES studies show Pb to be in the 4+ state while Tl is in the 3+ state, suggesting thereby that in this series, (x?y) approximately corresponds to the hole concentration. The in-plane Cu---O distance decreases with increase in x for all values of y. The apical Cu---O distance as well as the Tl(Pb)---O(2) distance show anomalies at x=0.5 in the series with y=0.25; at this composition, Tc also reaches a maximum. In general, the composition (value of x) at which the Tc of Tl1?yPbyY1?xCaxSr2Cu2O7 reaches a maximum depends on the Pb content and the maximum Tc itself increases with increase in y, reaching a value of 105 K at y=0.5. More interestingly, a maximum Tc occurs at an (x?y) value of not, vert, similar0.25, which is close to the hole concentration at maximum Tc in other cuprate superconductors containing two CuO2 layers.

Structure and properties of Tl0.5Pb0.5Sr2Gd2−xCexCu2O9−δ

A systematic study of the Tl0.5Pb0.5Sr2Gd2−xCexCu2O9−δ system has revealed the existence of a pure phase in the compositional. range 0.0≤x≤0.6 crystalizzing in the 1222 structure. It has an intersheet distance of approximately 6 Å, a value much higher than those found in other cuprates with double CuO2 sheets interleaved by a single fluorite layer. Superconductivity has been observed in the range 0.1≤x≤0.4 with a Tc of 45 K and a superconductive volume fraction up to 20% for the optimal composition. An interesting variation of the superconducting properties of the above system with the composition, i.e. cerium content, has also been noticed. A possible dependence of superconductivity on the coupling between CuO2 sheets in the layered cuprates has been pointed out to bring out a correlation between structure and properties.

Structure and superconducting properties of a new family of thallium cuprates, TlSr3−xLnxCu2O7

Cuprates of the formula TlSr3−xLnxCu2O7 (Ln=Pr, NdorY) derived from the hypothetical TlSr3Cu2O7 show superconductivity with Tcs up to 95 K when 0.5less, approximatex≤0.75, the x=1.0 compositions being insulators. Rietveld analysis of X-ray diffraction profiles has been carried out for two superconducting members of this family. The unit cell a-parameter, and hence the in-plane Cu-O distance, increases with increase in x. The Tc value decreases with increase in x or the in-plane Cu-O distance in all the series of cuprates. Superconductivity in the Tl1−yPbySr3−xNdxCu2O7 systems is found with the highest Tc of 95 K when y=0.2 and x=0.5. The in-plane Cu-O distances in all the cuprates studied fall in the range found in the Sr-class of cuprate superconductors.

Structure and temperature dependence of conductivity of Ag2.5Se‐Se composite

Rapid solidification of Ag‐53 at. % Se alloy resulted in the formation of a composite mixture of Ag2.5Se and Se. The microstructure consists of spherical Se grains of 2–20 μm size, randomly distributed in a matrix of Ag2.5 Se. The Se grains were found to be layered hexagonal while the Ag2.5 Se had an orthorhombic crystal structure. The unit cell size of this phase, however, was twice that reported for the equilibrium orthorhombic Ag2 Se compound. The conductivity σ variation with temperature in the range 80–320 K was found to be similar to that observed in degenerate semiconductors. The σ decreased from 295 Ω−1 cm−1 at room temperature to a saturation value of 70 Ω−1 cm−1 for temperatures <80 K. The results are discussed in terms of percolation conduction in the Ag2.5 Se phase.

A Rare Phenoxido/Acetato/Azido Bridged Trinuclear and an Unprecedented Phenoxido/Azido Bridged One-Dimensional Polynuclear Nickel(II) Complexes: Synthesis, Crystal Structure, and Magnetic Properties with Theoretical Investigations on the Exchange Mechanism

The reaction of a tridentate Schiff base ligand HL (2-(3-dimethylaminopropylimino)-methyl]-phenol) with Ni(II) acetate or perchlorate salts in the presence of azide as coligand has led to two new Ni(II) complexes of formulas Ni3L2(OAc)(2)(mu(1,1)-N-3)(2)(H2O)(2)]center dot 2H(2)O (1) and Ni2L2(mu(1,1)-N-3) (mu(1,3)-N-3)](n)(2). Single crystal X-ray structures show that complex 1 is a linear trinuclear Ni(II) compound containing a mu(2)-phenwddo, an end-on (EO) azido and a syn-syn acetato bridge between the terminal and the central Ni(II) ions. Complex 2 can be viewed as a one-dimensional (1D) chain in which the triply bridged (di-mu(2)-phenoxido and EO azido) dimeric Ni-2 units are linked to each other in a zigzag pattern by a single end-to-end (EE) azido bridge. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 16.51(6) cm(-1). The magnetic behavior of 2 can be fitted in an alternating ferro- and antiferromagnetic model J(FM) = +34.2(2.8) cm(-1) and J(AF) = -21.6(1.1) cm(-1)] corresponding to the triple bridged dinuclear core and EE azido bridge respectively. Density functional theory (DFT) calculations were performed to corroborate the magnetic results of 1 and 2. The contributions of the different bridges toward magnetic interactions in both compounds have also been calculated.

Molecular dynamic simulations of elastomer structure and its influence on anisotropic stress under time-varying strain

We investigate the evolution of polymer structure and its influence on uniaxial anisotropic stress under time-varying uniaxial strain, and the role of external control variables such as temperature, strain rate, chain length, and density, using molecular dynamics simulation. At temperatures higher than glass transition, stress anisotropy in the system is reduced even though the bond stretch is greater at higher temperatures. There is a significant increase in the stress level with increasing density. At higher densities, the uncoiling of the chains is suppressed and the major contribution to the deformation is by internal deformation of the chains. At faster rates of loading stress anisotropy increases. The deformation mechanism is mostly due to bond stretch and bond bending rather than overall shape and size. Stress levels increase with longer chain length. There is a critical value of the functionality of the cross-linkers beyond which the uniaxial stress developed increases caused primarily by bond stretching due to increased constraint on the motion of the monomers. Stacking of the chains in the system also plays a dominant role in the behaviour in terms of excluded volume interactions. Low density, high temperature, low values of functionality of cross-linkers, and short chain length facilitate chain uncoiling and chain slipping in cross-linked polymers.

Spatial variations of effective elastic thickness over the Ninetyeast Ridge and implications for its structure and tectonic evolution

We present new data on the strength of oceanic lithosphere along the Ninetyeast Ridge (NER) from two independent methods: spectral analysis (Bouguer coherence) using the fan wavelet transform technique, and spatial analysis (flexure inversion) with the convolution method. The two methods provide effective elastic thickness (T-e) patterns that broadly complement each other, and correlate well with known surface structures and regional-scale features. Furthermore, our study presents a new high resolution database on the Moho configuration, which obeys flexural isostasy, and exhibit regional correlations with the T-e variations. A continuous ridge structure with a much lower T-e value than that of normal oceanic lithosphere provides strong support for the hotspot theory. The derived T-e values vary over the northern (higher T-e similar to 10-20 km), central (anomalously low T-e similar to 0-5 km), and southern (low T-e similar to 5 km) segments of the NER. The lack of correlation of the T-e value with the progressive aging of the lithosphere implies differences in thermo-mechanical setting of the crust and underlying mantle in different parts of the NER, again indicating diversity in their evolution. The anomalously low T-e and deeper Moho (similar to 22 km) estimates of the central NER (between 0.5 degrees N and 17 degrees S) are attributed to the interaction of a hotspot with the Wharton spreading ridge that caused significant thermal rejuvenation and hence weakening of the lithosphere. The higher mechanical strength values in the northern NER (north of 0.5 degrees N) may support the idea of off-ridge emplacement and a relatively large plate motion at the time of volcanism. The low T-e and deeper Moho (similar to 22 km) estimates in the southern part (south of 17 degrees S) suggest that the lithosphere was weak and therefore younger at the time of volcanism, and this supports the idea that the southern NER was emplaced on the edge of the Indian plate. (C) 2013 Elsevier B.V. All rights reserved.

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2 `-bipyridine

The synthesis of the heterobinuclear copper-zinc complex CuZn(bz)(3)(bpy)(2)]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 angstrom. The complex is normal paramagnetic having mu(eff) value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants A(av) = 63 x 10(-4) cm(-1), characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g(parallel to) = 2.254 and g(perpendicular to) =2.071 and A(parallel to) = 160 x 10(-4) cm(-1). The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution. (C) 2014 Elsevier B.V. All rights reserved.

First principles DFT investigation Of Yttrium-decorated Boron-Nitride Nanotube: Electronic Structure and Hydrogen Storage

The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0 mu(B). Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.

I. The structure and properties of closed circular duplex DNA. II. Chemically interacting systems at equilibrium in a buoyant density gradient

I. The binding of the intercalating dye ethidium bromide to closed circular SV 40 DNA causes an unwinding of the duplex structure and a simultaneous and quantitatively equivalent unwinding of the superhelices. The buoyant densities and sedimentation velocities of both intact (I) and singly nicked (II) SV 40 DNAs were measured as a function of free dye concentration. The buoyant density data were used to determine the binding isotherms over a dye concentration range extending from 0 to 600 µg/m1 in 5.8 M CsCl. At high dye concentrations all of the binding sites in II, but not in I, are saturated. At free dye concentrations less than 5.4 µg/ml, I has a greater affinity for dye than II. At a critical amount of dye bound I and II have equal affinities, and at higher dye concentration I has a lower affinity than II. The number of superhelical turns, τ, present in I is calculated at each dye concentration using Fuller and Waring's (1964) estimate of the angle of duplex unwinding per intercalation. The results reveal that SV 40 DNA I contains about -13 superhelical turns in concentrated salt solutions.

The free energy of superhelix formation is calculated as a function of τ from a consideration of the effect of the superhelical turns upon the binding isotherm of ethidium bromide to SV 40 DNA I. The value of the free energy is about 100 kcal/mole DNA in the native molecule. The free energy estimates are used to calculate the pitch and radius of the superhelix as a function of the number of superhelical turns. The pitch and radius of the native I superhelix are 430 Å and 135 Å, respectively.

A buoyant density method for the isolation and detection of closed circular DNA is described. The method is based upon the reduced binding of the intercalating dye, ethidium bromide, by closed circular DNA. In an application of this method it is found that HeLa cells contain in addition to closed circular mitochondrial DNA of mean length 4.81 microns, a heterogeneous group of smaller DNA molecules which vary in size from 0.2 to 3.5 microns and a paucidisperse group of multiples of the mitochondrial length.

II. The general theory is presented for the sedimentation equilibrium of a macromolecule in a concentrated binary solvent in the presence of an additional reacting small molecule. Equations are derived for the calculation of the buoyant density of the complex and for the determination of the binding isotherm of the reagent to the macrospecies. The standard buoyant density, a thermodynamic function, is defined and the density gradients which characterize the four component system are derived. The theory is applied to the specific cases of the binding of ethidium bromide to SV 40 DNA and of the binding of mercury and silver to DNA.

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO2 thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO2 thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO2 thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances. (c) 2007 Elsevier B.V. All rights reserved.

Thickness dependence of structure and optical properties of silver films deposited by magnetron sputtering

A series of silver films with different thickness were prepared under identical conditions by direct current magnetron sputtering. The optical properties of the silver films were measured using spectrophotometric techniques and the optical constants were calculated from reflection and transmission measurements made at near normal incidence. The results show that the optical properties and constants are affected by films' thickness. Below the critical thickness of 17 nm at which Ag film forms a continuous film, the optical properties and constants vary significantly as the thickness of films increases and then tends to a stable value which is reached at 41 nm. X-ray diffraction measurements were carried out to examine the structure and stress evolution of the Ag films as a function of films' thickness. It was found that the interplanar distance of (111) orientation decreases when the film thickness increases and tends to be close to that of bulk material. The compressive strains also decrease with increasing thickness. (C) 2007 Published by Elsevier B.V.

Structure and anti-HIV activity of micrandilactones B and C, new nortriterpenoids possessing a unique skeleton from Schisandra micrantha

Two new highly oxygenated nortriterpenoids with a unique norcycloartane skeleton, micrandilactones B and C (1-2), were isolated from Schisandra micrantha; micrandilactone C ( 2) exhibited an EC50 value of 7.71 mu g/mL (SI > 25.94) against HIV-1 replication with minimal cytotoxicity, and the potent anti-HIV-1 activity and unique structural features of 2 make it a promising lead for therapeutic development of a new generation of anti-HIV drug.

The zooplankton population structure and their trend of variations in the southern of Caspian Sea (Iranian waters)

Caspian Sea has gone under a lot of changes due to human influences and the unwanted presence of a ctenophora Menomiopsis leidyi which has greatly changed the structure of planktons in the last recent years. Therefore, this study was carried out in order to determine these changes in the zooplankton community. the Sampling was done in 8 transacts in Astara, Anzali, Sefidrood, Tonekaboun, Noushahr, Babolsar, Amirabad and Bandar Torkaman coastal waters at 5 different depths including 5, 10, 20, 50 and 100 m. Sampling was carried out in four seasons of spring, summer, autumn and winter during 2008, 2009 and 2010 on board of R/V Gilan. Altogether, 12 species of zooplankton were identified in 2008, 22 species in 2009 and 14 species in 2010. The zooplankton included four groups: copepoda (4 species), cladocera (8species), rotatoria (10 species) and protozoa (2 species).The increase of diversity in 2009 was due to cladocera and rotatoria groups. The abundance of zooplankton in the spring was 5074 + 7807 ind/m3 more than other season in 2008. The abundance of copepoda in the summer reached the highest value of 3332 ind/m3 and since autumn the abundance gradually decreases and in the winter reached to the lowest value. The most abundance of cladocera was 797 ind/m3 in winter and decreased in summer and autumn. The abundance of rotatoria was 2189 ind/m3 in winter. rotifera and copepoda consisted the main population of Zooplanktons in the winter. The results of 2009 and 2010 showed that the abundance of zooplankton in winter was 2.6 fold of autumn, 1.6 fold of summer and 1.1 fold (1/9 fold in 2010)of spring. After increasing increased of temperature, phytoplankton, and zooplankton in summer, M.leidyi increased too. In the autumn M. leidyi reached to the highest rate and decreased zooplankton. The maximum population of zooplankton was in the layer 0-20 m and in the layer more than 20 meters, the abundance of zooplankton decreased very much. In 216 2008, 2009 and 2010, the abundance of zooplankton was 87, 77 and 77 percent in the layer 0-20 m respectively. In this study, the thermocline was observed in the layer 10 – 20 meters in the spring, that formed a thin layer but in the summer it was in the layer 20 to 50 meters. Temperature decreased between 11 to 15 oC in this layer. The variation of temperature between surfaces to bottom was 10 to 13 oC in spring, 19 to 21 in summer, about 9 oC in autumn and maximum 3 oC in winter. The most biomass of zooplankton was in the west. The biomass of zooplankton in central west and east of Southern of Caspian Sea was 54 %, 22 % and 24 % respectively in 2008, in 2009 was 48%, 33% and 20% respectively and in 2010 was 54 %, 29 % and 16 % respectively .The biomass decreased from west to east. The model of zooplankton designed by principal component analysis (PCA)and linear regression for Southern of Caspian Sea.