Observation of magnetic order of Cu-moment aroundx=0.12 in La2−x Ba x CuO4 and La2−x sr x CuO4 by μ+SR

Zero field positive muon spin rotation method ( ⁺SR) is applied on La_2–x Sr _x CuO₄ around forx=0.12 at which the high-T _c superconductivity (SC) is suppressed. The magnetically ordered state of Cu-moments, which is not a spin glass state but an antiferromagnetic like state, appears below 15 K for 0.105x0.120. The magnetic phase boundary is very similar to the one of the La_2–x Ba _x CuO₄ in which the structural transition from the low temperature orthorhombic (LTO) phase to the low temperature tetragonal (LTT) phase is observed aroundx=0.12. The present study suggests that there is no big difference of the electronic state of the CuO₂ plane between the La-Ba system and the La-Sr system and that the magnetic ordering of Cu-moments plays an important role for the suppression of the high-T _c SC aroundx=0.12 in both of the systems, although the LTO-LTT structural transition has not been observed yet in the La-Sr system.     

Key aspects of crystalline Mo-V-O-based catalysts active in the selective oxidation of propane

Mo-V-O-based complex metal oxide catalysts were synthesized hydrothermally for the first time, characterized structurally and tested in the selective oxidation of propane to acrylic acid, and the results obtained were compared on the basis of catalyst crystal structures in order to clarify key aspects of alkane selective oxidation over multifunctional metal oxide catalysts. The catalysts tested were black solids of rod-shaped crystals, which had a layer structure in the direction of fiber axis and various high dimensional arrangements of metal octahedra in the cross-section plane. A strong dependency on the octahedra arrangements and a facet dependency were observed, and the roles of metal elements in the course of selective oxidation of propane were clarified by comparing the catalytic performance of various Mo-V-O-based catalysts. We discuss the multi-functional character derived from high dimensional structures of the catalysts and mechanism of the selective oxidation of propane.     

Main-chain scissions of poly(methyl methacrylate) induced by chlorinated nitrosobenzenes as radical generators

The spin trap agent, 2,6-di-chloronitrosobenzene (DCNB), which is decomposed into a nitrogen monoxide and a chlorinated phenyl radical on slight warming, was known to act as a radical generator through hydrogen abstraction by the chlorinated phenyl radical from an adjacent molecule. An ESR spectrum was observed at room temperature from a poly(methyl methacrylate) (PMMA)-benzene solution after the addition of DCNB followed by a warming to ca 30°C. The radical concentration increased with time. The spectrum was assigned to the spin adducts of PMMA radicals generated and trapped by DCNB. Analyses of the spectra observed from normal PMMA and partially deuterated PMMA's indicated that the majority of the PMMA radicals were the chain-scission species

and a minority were

. It was concluded that the main-chain scissions in PMMA were caused by the radicals (D), which had been primarily produced by the chlorinated phenyl radicals. These ESR data are supported by the fact that a decrease in molecular weight of PMMA was observed after addition of DCNB, and further reinforced by the fact that a molecular weight estimated from the number of the scission radicals agreed fairly well with the measured molecular weight. Similar results were obtained when both tri-chlorinated nitrosobenzene and tetra-chlorinated nitrosobenzene were used instead of DCNB.     

A racemization test in peptide synthesis using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM)

Racemization of the C-terminal amino acid (Ala) has been studied in various solvents during coupling between 4-methoxybenzyloxycarbonyl (Z(OMe))-Gly-L-Ala-OH and phenylalanine benzyl ester (H-Phe-OBzl) with 4-(4,6-dimethoxy-1,3,5-thiazin-2-yl)-4-methylmorpholinium chloride (DMT-MM). The reaction occurred without substantial racemization in AcOEt, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), CH3CN, and 2-PrOH, while a slight racemization was observed in dimethyl sulfoxide (DMSO), EtOH, and MeOH. The extent of racemization may correlate with the polarity of the solvents.     

One electron transfer mechanism in the enzymatic oxygenation of sulfoxide to sulfone promoted by a reconstituted system with purified cytochrome p-450

A kinetic study on enzymatic S-oxygenation of sulfoxides to sulfones was carried out by a reconstited system with purified cytochrome P-450. A linear correlation observed between log(Vmax)'s and the one-electron oxidation potentials of sulfoxides suggests that the oxygenation of sulfoxides proceeds via one electron transfer process to the active “oxenoid” intermediate of the enzyme.