The molecular dynamics study of lithium ion conduction in phosphate glasses and the role of non-bridging oxygen

Molecular dynamics (MD) simulation of lithium phosphate (Li2O-P2O5) glasses with varying Li2O content has been carried out. Two different P-O distances corresponding to phosphorus coordination with bridging oxygen (BO) and non-bridging oxygen (NBO) were identified in the simulated glasses. NBO-BO interconversion or bond switching was noted, which results in a dynamic equilibration of the tetrahedral phosphate units (P-n, n = 1,3 indicates the number of bridging oxygen atoms in the coordination of phosphorus). The NBO-BO bond switching is mildly activated with an effective activation barrier of 0.03-0.05 eV. Lithium ion jumps do not appear to be strongly coupled to bond switching. But the number of Li+ ions coordinated to an optimum number of NBOs and the number of Li+ ions jumping out of their sites appear to be correlated. Detailed analysis was made of the dynamics of P-n species and new insights have been obtained regarding ion migration in network-modified phosphate glasses.

Theory of coexisting charge and spin-density waves in (TMTTF)(2)Br, (TMTSF)(2)PF6 and alpha-(BEDT-TTF)(2)MHg(SCN)(4)

We discuss a recently formulated microscopic theory of the unusual coexistence of spin density waves (SDWs) and charge density waves (CDWs) that has been seen in recent experiments on (TMTTF)2Br, (TMTSF)2PF6 and α-(BEDT-TTF)2MHg(SCN)4.

Chromatographic methods for determination of nimesulide and for stability studies

Simple and rapid HPLC, GC, and TLC procedures have been developed for detection and determination of nimesulide, a non-pharmacopeial drug, in preformulation and dosage form. Use of these techniques has enabled separation of impurities and the precursor in the bulk material and in formulations. Isocratic reversed-phase HPLC was performed on a C-18 column with methanol-water-acetic acid, 67:32:1 (v/v), as mobile phase and UV detection at 230 nm. Calibration curves were linear over the concentration range 100-1000 mug mL(-1) with a good correlation coefficient (0.9993) and a coefficient of variation of 1.5%. Gas chromatography was performed on an OV-17 packed column with temperature programming and flame-ionization detection. The lower limit of determination by HPLC and GC was 4 ppm. Thin-layer chromatography of nimesulide was performed on silica gel G with toluene-ethyl acetate, 8:2, as mobile phase. Stability testing of the drug was performed under different temperature, humidity, and UV-radiation conditions.

Development of a clean bioelectrochemical process for leaching of ocean manganese nodules

Through the application of negative reduction potential significant reduction of manganic and iron oxides in the ocean manganese nodules can be achieved, liberating the occluded copper, nickel and cobalt for easy dissolution in an acid medium. Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Thiobacillus ferrooxidans and Thiobacillus thiooxidans at the above negative applied dc potentials resulted in significant dissolution of copper, nickel and cobalt in 1 M H2SO4. The role of galvanic interactions in the bioleaching of ocean manganese nodules in the presence of T thiooxidans is also discussed, (C) 2002 Published by Elsevier Science Ltd.

Hydrothermal synthesis and structure of organically templated one-dimensional and three-dimensional iron fluorophosphate

Two new open-framework iron fluorophosphates, [C(4)N(2)H(12)](0.5) [FeF(HPO(4))(H(2)PO(4))] (I) and [C(4)N(2)H(12)][Fe(4)F(2)(H(2)O)(4)(PO(4))(4)]. 0.5H(2)O (II), were synthesized hydrothermally using piperazine as a templating agent. The structures were determined by single-crystal X-ray diffraction. Compound I crystallizes in the orthorhombic space group Pbca, a = 7.2126(2) Angstrom, b = 14.2071(4) Angstrom, c = 17.1338(2) Angstrom, Z = 8. The structure is composed of infinite anionic chains of [FeF(HPO(4))(H(2)PO(4))](n)(-) built by trans-fluorine sharing FeF(2)O(4) octahedra. These chains are similar to those found in tancoite-type minerals. Compound II crystallizes in the monoclinic space group P2(1)/n, a = 9.9045(3) Angstrom, b = 12.3011(3) Angstrom, c = 17.3220(4) Angstrom, beta = 103.7010(10)degrees, Z = 4. The structure of compound II has a three-dimensional (3D) architecture with an eight-membered channel along the b axis, in which protonoted piperazine molecules reside. The complex framework is built from two types of secondary building unit (SBU): one hexamer [Fe(3)F(2)(H(2)O)(2)(PO(4))(3)] (SBU6), and one dimer [FeO(4)(H(2)O)(2)PO(4)] (SBU2). The vertex sharing between these SBUs create the 3D structure.

Seismic passive earth pressure coefficients using the method of characteristics

The method of characteristics was used to generate passive earth pressure coefficients for an inclined wall retaining cohesionless backfill material in the presence of pseudostatic horizontal earthquake body forces. The variation of the passive earth pressure coefficients K-pq and K-pgamma with changes in horizontal earthquake acceleration coefficient due to the components of soil unit weight and surcharge pressure, respectively, has been obtained; a closed-form solution for K-pq is also provided. The passive earth resistance has been found to decrease sharply with an increase in the magnitude of horizontal earthquake acceleration. The computed passive earth pressure coefficients were found to be the lowest when compared to all of the previous solutions available in the literature.

Twisted aromatics, 9-anthryl and 1-pyrenyl terpyridines organize into novel multi-directional 'ladder-like' motifs in the solid state

9-Anthryl and 1-pyrenyl terpyridines (1 and 2, respectively), key precursors for the design of novel fluorescent sensors have been synthesized and characterized by H-1 NMR, mass spectroscopy and X-ray crystallography. Twisted molecular conformations for each 1 and 2 were observed in their single crystal structures. Energy minimization calculations for the 1 and 2 using the semi-empirical AM1 method show that the 'twisted' conformation is intrinsic to these systems. We observe interconnected networks of edge-to-face CH...pi interactions, which appear to be cooperative in nature, in each of the crystal structures. The two twisted molecules, although having differently shaped polyaromatic hydrocarbon substituents, show similar patterns of edge-to-face CH...pi interactions.The presently described systems comprise of two aromatic surfaces that are almost orthogonal to each other. This twisted or orthogonal nature of the molecules leads to the formation of interesting multi-directional ladder like supramolecular organizations. A combination of edge-to-face and face-to-face packing modes helps to stabilize these motifs. The ladder like architecture in 1 is helical in nature. (C) 2002 Published by Elsevier Science B.V.

Equilibrium and relaxation in turbulent wakes

In order to study the memory of the larger eddies in turbulent shear flow, experiments have been conducted on plane turbulent wakes undergoing transition from an initial (carefully prepared) equilibrium state to a different final one, as a result of a nearly impulsive pressure gradient. It is shown that under the conditions of the experiments the equations of motion possess self-preserving solutions in the sense of Townsend (1956), but the observed behaviour of the wake is appreciably different when the pressure gradient is not very small, as the flow goes through a slow relaxation process before reaching final equilibrium. Measurements of the Reynolds stresse show that the approach to a new equilibrium state is exponential, with a relaxation length of the order of 103 momentum thicknesses. It is suggested that a flow satisfying the conditions required by a self-preservation analysis will exhibit equilibrium only if the relaxation length is small compared with a characteristic streamwise length scale of the flow.

Decomposition temperatures of Cu2Ln2O5 (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds

The equilibrium decomposition temperatures of Cu2Ln2O5 (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds have been measured using a combined DTA-TGA apparatus under a flowing Ar + O2 gas mixture, in which the partial pressure of oxygen was controlled at 5.0 × 103 Pa. The Cu2Ln2O5 compounds yield Ln2O3 and Cu2O on decomposition. The decomposition temperature increases monotonically with the atomic number of the lanthanide element. This suggests that the stability of the Cu2Ln2O5 compounds with respect to the component binary oxides increases with decreasing radius of the Ln3+ ion.

Efficient syntheses of benzothiazepines as antagonists for the mitochondrial sodium-calcium exchanger: Potential therapeutics for type II diabetes

Type II diabetes mellitus is a chronic metabolic disorder that can lead to serious cardiovascular, renal, neurologic, and retinal complications. While several drugs are currently prescribed to treat type II diabetes, their efficacy is limited by mechanism-related side effects (weight gain, hypoglycemia, gastrointestinal distress), inadequate efficacy for use as monotherapy, and the development of tolerance to the agents. Consequently, combination therapies are frequently employed to effectively regulate blood glucose levels. We have focused on the mitochondrial sodium-calcium exchanger (mNCE) as a novel target for diabetes drug discovery. We have proposed that inhibition of the mNCE can be used to regulate calcium flux across the mitochondrial membrane, thereby enhancing mitochondrial oxidative metabolism, which in turn enhances glucose-stimulated insulin secretion (GSIS) in the pancreatic beta-cell. In this paper, we report the facile synthesis of benzothiazepines and derivatives by S-alkylation using 2-aminobenzhydrols. The syntheses of other bicyclic analogues based on benzothiazepine, benzothiazecine, benzodiazecine, and benzodiazepine templates are also described. These compounds have been evaluated for their inhibition of mNCE activity, and the results from the structure-activity relationship (SAR) studies are discussed.

Mathematical model of COREX melter gasifier: Part I. Steady-state model

The COREX melter gasifier is a countercurrent reactor to produce liquid iron. Directly reduced iron (DRI), noncoking coal, and other additives are charged to the melter gasifier at their respective temperatures, and O-2 is blown through the tuyeres. Functionally, a melter gasifier is divided into three zones: a moving bed, fluidized bed, and free board. A model has been developed for the moving bed, where the tuyere region is two-dimensional (2-D) and the rest is one-dimensional (1-D). It is based on multiphase conservation of mass, momentum, and heat. The fluidized bed has been treated as 1-D. Partial equilibrium is calculated for the free board. The calculated temperature of the hot metal, the top gas, and the chemistry of the top gas agree with the reported plant data. The model has been used to study the effects of bed height, injection of impure O-2, coal chemistry, and reactivity on the process performance.

Synthesis based on cyclohexadienes Part 36: an efficient methodology for the construction of spiro[4.5]decanes: a formal synthesis of acorone

An efficient strategy for the contruction of spiro[4.5] decanes is described and involves a bridgehead substitution of a methoxyl group by a methyl group followed by an oxidative cleavage of the tricyclo[5.2.2.0(1,5)] undecane 25 to produce the spiro[4.5] decanes 31 & 32 which are intermediates in the synthesis of acorone. A novel one-pot conversion of alpha-methoxy carboxylic acid to alpha-methyl carboxylic acid is described.

A Note On The Effect Of Short And Long Laminar Separation-Bubbles On Desinent Cavitation

Earlier desinent cavitation studies on a 1/8 caliber ogive by one of the authors (J. W. H.) showed a sudden change in the magnitude of the desinent cavitation number at a critical velocity. In the present work it is shown by means of oil-film flow visualization that below the critical velocity a long laminar separation bubble exists whereas above the critical velocity the laminar separation bubble is short. Thus the desinent cavitation characteristics of a 1/8 caliber ogive are governed by the nature of the viscous flow around the body.