Superconductivity in Sr<Subscript>0.75</Subscript>Y<Subscript>0.75</Subscript>Ba<Subscript>1.5</Subscript>Cu<Subscript>3</Subscript> O<Subscript>7−<Emphasis Type="Italic">d</Emphasis></Subscript> compounds

The effect of simultaneous Sr substitution at the Ba and Y sites has been studied in the Sr_0.75Y_0.75Ba_1.5Cu₃O_7–dsystem. Attempts to replace 25% Y and 25% Ba have been successful and superconductivity was observed above 78 K for Sr_0.75Y_0.75Ba_1.5Cu₃O_7–d compound with high oxygen content, i.e., O_6.76, and having orthorhombic crystal symmetry. The compound was treated in argon gas at 800°C to reduce the oxygen content and to induce some structural changes. The Sr_0.75Y_0.75Ba_1.5Cu₃O_6.1 compound thus obtained has tetragonal symmetry and low oxygen content, O_6.1. It has also shown superconductivity at 28 K. The paper presents a careful comparison of the structural and electrical properties and infrared absorbance spectra of the two compounds with the same metallic composition, Sr_0.75Y_0.75Ba_1.5Cu₃, but with different oxygen content and crystal symmetry. The study clearly establishes the occurrence of superconductivity in tetragonal Sr-substituted (both at Y and Ba sites in) YBCO.     

An approach to developing a force field for molecular simulation of martensitic phase transitions between phases with subtle differences in energy and structure

d,l-Norleucine is one of only a few molecules whose crystals exhibit a martensitic or displacive-type phase transformation where the emerging phase shows a topotaxial relationship with the parent phase. The molecular mechanism for such phase transformations, particularly in molecular crystals, is not well understood. Crystalline phases that exhibit displacive phase transitions tend to be very similar in structure and energy. Consequently, the development of a force field for such phases is challenging as the phase behavior is determined by subtle differences in their lattice energies and entropies. We report an approach for developing a force field for such phases with an application to d,l-norleucine. The proposed procedure includes calculation of the phase diagram of the crystalline phases as a function of temperature to identify the best force field. d,l-Norleucine also presents an additional problem since in the solid state it exists as a zwitterion that is unstable in vacuo and therefore cannot be characterized using high-level ab initio calculations in the gas phase. However, a stable zwitterion could be obtained using Onsager's reaction-field continuum model for a solvent (SCRF) using both Hartree-Fock and density functional theory. A number of force fields and the various sets of partial charges obtained from the SCRF calculations were screened for their ability to reproduce the crystal structures of the two known phases, alpha and beta, of d,l-norleucine. Selected parameter sets were then employed in free energy minimizations to identify the best set on the basis of a correct prediction of the alpha-beta phase transition. The Williams' nonbonded parameters combined with partial charges from SCRF-Polarized Continuum Model calculation were found to reproduce the structures of the phases accurately and also maintained their stability in extended molecular dynamics simulations in the Parrinello-Rahman constant stress ensemble. Moreover, we were also able to successfully simulate the phase transformation of the beta- to the alpha-phase. The identified force field should enable detailed studies of the phase transformations exhibited by crystals of d,l-norleucine and hence enhance our understanding of martensitic-type transformations in molecular crystals.     

Pyrrolidinones derived from (S)-pyroglutamic acid: penmacric acid and analogues

Alkylation reactions using alpha-halolactams or lactam enolates derived from bicyclic lactam templates can proceed with high endo- or exo- diastereoselectivity respectively. In the latter case, stereochemical correction by means of enolate generation and hindered phenol quench is possible with moderate efficiency. This protocol has been applied to the synthesis of protected penmacric acid and its analogues.     

Manganese Dioxide Mediated Stereoselective, One-step Synthesis of Novel Steroidal (6R)-Spiro-1’,2’,4’-triazoline-3’-thiones

Oxidative cyclization of 5α-cholestan-6-one thiosemicarbazone (1), its 3β-chloro (2) and 3β-acetoxy (3) analogues with active manganese dioxide at room temperature afforded selectively the corresponding (6R)-spiro-1’,2’,4’-triazoline-3’-thiones 4—6. This synthesis has the advantages of mild reaction conditions, easy handling, easily available reagent and high yields. The products have been characterized by analytical and spectral data.     

硫酸溶液中胶束催化Ce(IV)氧化D-甘露糖

Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in cerium(Ⅳ), which decreased with increasing [H2SO4]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (Ⅳ) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was reactive form of cerium (Ⅳ). From the kinetic data, micelle-cerium (Ⅳ) binding and rate constants in micellar medium were evaluated.The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: --d[Ce(Ⅳ)]= k1Kcl[D-mannose] [Ce(Ⅳ)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed.     

Morphological,thermal, and conductivity studies of poly(methyl methacrylate)/polyaniline dodecylbenzenesulfonate blends

Soluble in organic solvent polyaniline (PANI) was prepared using DBSA as a functional dopant. Miscibility was maximized for PMMA with hydroquinone. Transmission electron micrographs showed lowest level of phase separation. Thermal studies by differential scanning calorimetry show some peak shifts which indicate the miscibility of two polymers. The formations of new bonds are also confirmed by Fourier transformation infrared spectroscopy. Electroconductivity increased with increase of content of doped PAN1, showing percolation threshold at 3 wt %.     

Diethyl 1-(p-fluoro­phenyl)-5-oxo-3-(2-thienyl)­pyrrolidine-2,2-di­carboxyl­ate

In the title compound, C₂₀H₂₀FNO₅S, the pyrrolidine ring adopts an envelope conformation. The fluoro­phenyl and thio­phene rings are individually planar. The molecular and crystal structures are stabilized by intra- and intermolecular C—H⋯O interactions.     

$QTAG$-Modules whose $h$-Pure-$S$-High Submodules Have Closure

A right module $M$ over an associative ring $R$ with unity is a $QTAG$-module if every finitely generated submodule of any homomorphic image of $M$ is a direct sum of uniserial modules. This article considers the closure of $h$-pure-$S$-high submodules of $QTAG$-modules. Here, we determine all submodules $S$ of a $QTAG$-module $M$ such that each closure of $h$-pure-$S$-high submodule of $M$ is $h$-pure-$\overline{S}$-high in $\overline{M}$. A few results of this theme give a comparison of some elementary properties of $h$-pure-$S$-high and $S$-high submodules.     

Density, Viscosity, Refractive Index, and Speed of Sound in Binary Mixtures of Pyridine and 1-Alkanols (C6, C7, C8, C10) at 303.15 K

The densities (ρ), viscosities (η), refractive indices (nD), and speeds of sound (u), of binary mixtures of pyridine with 1-hexanol, 1-heptanol, 1-octanol and 1-decanol, including those of pure liquids, were measured over the entire composition range at 303.15 K and atmospheric pressure. From these experimental data, the values of excess molar volumes (VE), deviations in isentropic compressibilities (Δks), viscosities (Δh), molar refractions (ΔRm), apparent and partial molar volumes (Vf,2 and ), apparent and partial molar compressibilities (Kf,2 and ), of alkanols in pyridine and their corresponding deviations (ΔV and ΔK) were calculated. The variations of these parameters with composition of the mixtures suggest that the strength of interactions in these mixtures follow the order: 1-hexanol＞1-heptanol＞1-octanol＞1-decanol. All the excess and deviation functions were fitted to Redlich-Kister polynomial equation to determine the fitting coefficients and the standard deviations.