On non-linear non-equilibrium statistical mechanics

The exact equations of motion for slow variables, which characterize a macroscopic system far from equilibrium, are derived with the help of a new time-dependent projection operator. The present formalism is a natural extension of Mori's approach to the non-linear region far from equilibrium, or of Kawasaki-Gunton's approach to quantal systems.     

Delayed formation of muon-containing species in organic liquids observed by spin resonance technique

The resonance technique has been applied to observe diamagnetic muons and, for the first time by the resonance, Mu-substituted radicals in organic liquids under strong decoupling magnetic fields. In benzoquinone solutions in benzene the relaxation of Mu-cyclohexadienyl radicals through reaction with quinone was directly observed by the radical resonance technique. The product of this reaction was then observed by the diamagnetic muon resonance as a slow formation. Similar slow formation was observed for diamagnetic muons in neat CS₂ and for Mu-radicals in benzene and styrene. Such slow formation can never be observed by the rotation technique due to dephasing problem, and thus the previous method is expected to provide new source of information on slow reaction dynamics of muon containing species.     

Enantiospecific synthesis of optically pure (3s)-hydroxy esters by the stereocontrolled yeast reduction of α-sulfenyl-β-ketoesters

Stereocontrol in Baker's yeast reduction of β-ketoesters was successfully achieved by introducing the sulfenyl group at α-position of the esters to afford optically pure (S)-β-hydroxy esters.     

The deoxygenation in the catalytic hydrogenolysis of styrene oxides

In order to obtain information on deoxygenation in the hydrogenolysis of epoxides, a series of substituted styrene oxides were hydrogenolysed using Raney Ni, Pd and Pt as catalysts. Over Raney Ni, these styrene oxides gave ethylbenzenes (30–50%) as well as 2-phenylethanols. The ethyl-benzenes were proved to be producedvia the corresponding styrenes. These deoxygenations can be explained by the previously proposed mechanism involving the radical cleavage reaction. The hydrogenolyses over Pd gave selectively 2-phenylethanols. Over PtO₂, the deoxygenations were less than 10% except 3,4-dichlorostyrene oxide (V) which gave 3,4-dichloroethylbenzene in 75% yield. However, the significant deoxygenations were observed in all hydrogenolyses over Pt-black. The ethylbenzenes were proved to be produced directly from the corresponding styrene oxides, but not from 1-phenylethanols as proposed by Park and Fuchs. These deoxygenations are considered to occurvia styrenes bytrans-β-elimination. The difference in behaviour over Pt catalysts can be ascribed to the alkaline substances contained in the catalyst. The significant deoxygenation in the hydrogenolysis of V over PtO₂ can be explained by the effect of a trace of HCl produced from the substrate and/or products.     

Effect of spin fluctuations on the electrical resistivity in the pressure-induced metallic phase of 7 at.% Co-doped NiS2

The electrical resistivity measurements were made from 4.2 K to room temperature on 7 at.% Co-doped NiS₂ at pressures from 19 to 71 kbar. T²-dependence of electrical resistivity due to the spin fluctuations was found, and the pressure dependence of its coefficient was determined.     

Determination of sodium dodecylbenzene sulfonate in ternary mixtures by curie-point pyrolysis gas chromatography coupled to multivariate analysis

Summary Multivariate analysis was used to develop a viable method for determination of sodium dodecylbenzene sulfonate (DBS) by Curie-point pyrolysis gas chromatography. The pyrograms obtained were normalized against a maximum peak area and peak height. Normalized values were used for Quantification IV, which is one of the multivariate analysis methods, to select useful values initially. Then cluster analysis was carried out using both the selected values and their deviations. This method corresponds to qualitative analysis and indicates which data-base is similar to the sample. On the basis of this data-base, calibration data-bases are chosen. Principal component analysis (PCA) was performed using the calibration data-base and a set of sample data simultaneously. The principal component scores and contribution coefficients obtained were used to construct a calibration curve from which the DBS content of the sample was calculated. The results are in fair agreement with theoretical values.     

Circular dichroism of tail-to-tail bisbenzyliso-quinoline and the absolute configuration of daurisoline isolated from Menispermum dauricum

Since two asymmetric centres are usually present in the bisbenzylisoquinolines, the circular dichroism is known to be an important method to elucidate their stereochemistry. We studied the relationships of the CD spectra with the stereochemistry of synthetic RR-(1), SS-(2), RS-daurisoline (3) and SR-daurisoline (4). By comparision of the CD spectrum of natural daurisoline (1) from Menispermum dauricum (Menispermaceae) with those of synthetic enantiomers, the absolute configuration was established as RR-daurisoline (1).