Thermal behavior of ternary Sm2Fe17Nx magnets

The Mössbauer spectra of Sm₂Fe₁₇N_x, prepared by the nitrogenation of Sm₂Fe₁₇ powders in an ammonia and hydrogen atmosphere, were observed at elevated temperatures to shed light on the thermal behavior of nitrogen in the compounds Sm₂Fe₁₇N_x. It was found that there were large differences in thermal behavior between the starting Sm₂Fe₁₇, crystalline Sm₂Fe₁₇N_x (x≈1.7) and amorphous Sm₂Fe₁₇N_x(x～7). The thermal decomposition behavior of Sm₂Fe₁₇N_3.2, developed as one of the most promising hard magnetic materials, was found to be different under different atmospheres.     

High performance liquid chromatography equipped with a cathodic detector and column-switching device as a high-throughput method for a phosphatase assay with p-nitrophenyl phosphate

A preparative high-speed counter-current chromatography (HSCCC) method for isolation and purification of coumarin compounds from the Chinese medicinal plant Peucedanum decursivum (Miq.) Maxim (Zihuaqianhu in Chinese) was successfully established by using light petroleum-ethyl acetate-methanol-water (5:5:7:4, v/v) as the two-phase solvent system. The upper phase of light petroleum-ethyl acetate-methanol-water (5:5:7:4, v/v) was used as the stationary phase of HSCCC. Nodakenetin (2.8 mg), 6.1 mg of Pd-C-IV, 7.3 mg of Pd-D-V, 4.7 mg of ostruthin, 7.8 mg of decursidin and 11.2 mg of decursitin C with the purity of 88.3%, 98.0%, 94.2%, 97.1%, 97.8% and 98.4%, respectively, were separated successfully in one-step separation from 150 mg of crude sample from P. decursivum (Miq.) Maxim. After purified by HSCCC again with light petroleum-ethyl acetate-methanol-water (5:5:4:5, v/v) as the two-phase solvent system, the purity of (I) can reach 99.4%. The structures of all the compounds were identified by 1H NMR and 13C NMR.     

Highly diastereoselective chemoenzymatic synthesis of (2′R)- and (2′S)-2′-deoxy[2′-H]guanosines

In an effort to develop an efficient synthetic method of highly diastereoselective (2′R)- and (2′S)-2′-deoxy[2′-²H]guanosines, chemoenzymatic conversion was investigated. The synthesis of (2′R > 98% de)-2′-deoxy[2′-²H]guanosine was achieved by biological transdeoxyribosylation using (2′R > 98% de)-2′-deoxy[2′-²H]uridine, 2,6-diaminopurine, and Enterobacter aerogenes AJ-11125, followed by treatment with adenosine deaminase. (2′S > 98% de)-2′-Deoxy[2′-²H]guanosine was synthesized from (2′S > 98% de)-2′-deoxy[2′-²H]uridine and 2,6-diaminopurine using thymidine phosphorylase and purine nucleoside phosphorylase instead of E. aerogenes AJ-11125.     

Palladium(0)-catalyzed stereoselective cyclization of allenenes: divergent synthesis of pyrrolidines and 3-azabicyclo[3.1.0]hexanes from single allenenes

Two novel palladium(0)-catalyzed cyclizations of allenenes are described. Treatment of allenenes such as N-(1-alkyl-2,3-butadienyl)-N-allylsulfonamide with an aryl halide and K(2)CO(3) in the presence of a catalytic amount of Pd(PPh(3))(4) in dioxane affords 2,3-cis-pyrrolidines in a stereoselective manner. In sharp contrast, cyclization of the same allenenes using catalytic Pd(2)(dba)(3) x CHCl(3) in the presence of allyl methyl carbonate in CH(3)CN leads to stereoselective formation of a 3-azabicyclo[3.1.0]hexane framework in moderate yields.     

Novel properties of molecular assemblies of isoprenoid surfactants

Unlike micelles of straight hydrocarbon chain-surfactants, isoprenoid surfactants, CH₃ [CH(CH₃)CH₂CH₂CH₂]₃ CH(CH₃)CH₂–R (R=CH₂N⁺ (CH₃)₃ Br^–, CH₂OPO₃H^– Na⁺, CH₂OSO ₃ ^– Na⁺, CO ₂ ^– Na⁺), gave large globular and cellular assemblies in water which could be observed directly by transmission electron microscopy; critical micelle concentration of 0.31.4×10^–3 M at 20°C, aggregation number of 215×10⁴, and diameter of 200–2000 Å. A basic structure of the assemblies was a thin layer with a thickness (about 30 Å) which was close to the molecular length of the surfactants. The assemblies were decomposed during gel column chromatography; viz., they were not as stable as the liposomes of lecithins. The morphology was discussed in conjunction with a steric effect of the isoprenoid chain.     

Marstomentosides O-T polyoxypregnane glycosides from Marsdenia tomentosa

Thirteen pregnane glycosides were isolated from fresh leaves of Marsdenia tomentosa collected in the Fukuyama district. Of these, six were glycosides previously obtained from the same plant collected in the Fukuoka district and one from another Asclepiadaceous plant. The structures of the six new glycosides were determined by spectrometric method.     

Synthesis, conformation and PKC isozyme surrogate binding of indolinelactam-Vs, new conformationally restricted analogues of (−)-indolactam-V

New conformationally restricted analogues of tumor promoter (−)-indolactam-V (1), indolinelactam-Vs (8, 11) and their hexyl derivatives at position 1 or 7 (9, 10, 12, 13), were synthesized from 1. (3R)-Indolinelactam-V (8) adopted a conformation similar to the twist form of 1 with a cis amide, while the conformation of (3S)-indolinelactam-V (11) was close to that of the sofa form of 1 with a trans amide. 7-Hexyl derivatives of 8 and 11 (10, 13) showed binding affinities for C1 domains of protein kinase C (PKC) isozymes compared to 1, but exhibited little selectivity among these PKC isozymes. However, introduction of the hexyl group at position 1 of 8 and 11 significantly enhanced their binding selectivity for novel PKC isozymes. The best selectivity for novel PKC isozymes was observed in (3S)-1-hexylindolinelactam-V (12) with a sofa-like conformation. These results suggest that a sofa-restricted analogue of 1 with a hydrophobic chain at an appropriate position would be a promising lead for designing agents with a high selectivity for novel PKC isozymes.     

Charge compensation and oxidation in NaxCoO2−δ and LixCoO2−δ studied by XANES

A comparative study on the oxidation and charge compensation in the A_xCoO_2−δ systems, A=Na (x=0.75, 0.47, 0.36, 0.12) and Li (x=1, 0.49, 0.05), using X-ray absorption spectroscopy at O 1s and Co 2p edges is reported. Both the O 1s and Co 2p XANES results show that upon removal of alkali metal from A_xCoO_2−δ the valence of cobalt increases more in Li_xCoO_2−δ than in Na_xCoO_2−δ. In addition, the data of O 1s XANES indicate that charge compensation by oxygen is more pronounced in Na_xCoO_2−δ than in Li_xCoO_2−δ.