Preparation of Y2Ba4Cu7O15-δ Superconductor without High Oxygen Pressure

The synthesis of bulk Y₂Ba₄Cu₇O_15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y₂Ba₄Cu₇O_15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y₂Ba₄Cu₇O_15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described.     

Application of an integrated microchip system with capillary array electrophoresis to optimization of enzymatic reactions

In this work, a combination of complementary metal-oxide semiconductor (CMOS) microchip system with capillary array electrophoresis (CAE) is demonstrated as a system for optimizing conditions for enzymatic reaction. Dimethylacridinone (DDAO)-phosphate substrate and alkaline phosphatase conjugate were selected for the enzymatic reaction, which was applicable to the enzyme-linked immunosorbent assay (ELISA) technique. Laser-induced fluorometry with a miniature semiconductor laser was used to detect the enzymatic products. The speed of the enzymatic reaction between the DDAO-phosphate and the alkaline phosphatase conjugate was investigated as a function of reaction time. The microchip-CAE detection system could determine the pH condition and the concentration of enzyme that are suitable for rapid and low-cost analysis. This result shows the feasibility of using the microchip-CAE system for application to miniaturized screening systems.     

Diels—Alder reaction. Effect of internal and external factors on the reactivity of diene—dienophile systems

The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids.     

Halex reactions of aromatic compounds catalysed by 2-azaallenium, carbophosphazenium, aminophosphonium and diphosphazenium salts: a comparative study

An increasing number of biologically active compounds in the pharma and agro-chemical sector contain carbon fluorine bonds. One of the most common methods to introduce fluorine into intermediates is the well-investigated halogen-exchange reaction, in which chloro- and bromoaromatics activated towards nucleophilic substitution, react with a fluoride source to yield the corresponding fluoroarenes. In general, the reaction is supported by phase-transfer catalysts. The use of a new class of very active phase-transfer catalysts gives the possibility of substituting even halogens with weak activation giving a convenient access to interesting compounds that are not available so far and opening up new synthetic routes in Halex chemistry. Our new classes of catalysts, CNC⁺ (1a), PNC⁺ (2a) and several different approaches presented by other groups are described and experimental results discussed.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

The modulation of face-face π-π interactions in Lewis acid catalysis

The enantiomeric excess observed for the exo-adduct from the Lewis acid catalysed Diels-Alder reaction between cyclopentadiene and methacrolein can be increased up to 21% by simple modification of the electronics of the aromatic ring in a series of stilbene-derived diol ligands, suggesting that the proposed face-face π-π interaction between the catalyst and the dienophile can be modulated by altering the electron density on the aromatic ring.     

Multipeak distributions of first passage times in bistable dynamics in a model of a thermochemical system.

A master equation is used to study transitions between the stable limit cycle and stable focus in the two-variable bistable system. The distribution function of the mean first passage time between these attractors and the relative dispersion of the mean first return time from the stable focus to itself as a function of the intensity of fluctuations are calculated and discussed. A coherence resonance is observed for the return time from the focus to itself.     

Total synthesis of the marine alkaloid halitulin

The structure of the strongly cytotoxic marine alkaloid halitulin (1) has been confirmed by total synthesis and its absolute configuration determined as (15S). The synthesis follows a strategy previously reported by one of us and uses an efficient preparation of the quinoline-7,8-diol unit by modified Baeyer-Villiger and Skraup reactions. The O-benzyl protecting groups were removed in the last step of the synthesis by transfer hydrogenolysis without concomitant reduction of the quinoline ring. The method can be applied for the synthesis of halitulin analogues.     

Exact solutions for Belousov-Zhabotinskii reaction-diffusion system

Abstract. We consider the following simplified model for the Belousou-Zhabotinskii(B-Z)reaction:     

Cu~(2+)与三磺基四苯基啿卟啉配位反应研究

利用吸收光谱法和直流极谱法研究了Cu~(2+)的还原状态、抗坏态、抗坏血酸浓度及溶解氧对Cu~(2+)与三磺基四苯基卟啉配位反应的影响。结果表明Cu~(2+)与三磺基四苯(?)基四苯基卟啉配位反应的可能机制为抗坏血酸首先将高价铜还原为亚铜,亚铜离子与配位剂生成对氧成对氧敏感的不稳定中间体Cu~(Ⅰ)——三磺基四:苯基卟啉配合物,立即又被溶解氧氧化为Cu(Ⅱ)——Ⅱ)——三磺基四苯基卟啉配合物。