Oxidative transformation of tryptophan to 3-(2-aminophenyl)-2-pyrrolidone and kynurenine

Oxytryptophans 3, which are readily obtained by dye-sensitized photooxygenation of tryptophan followed by acid treatment, undergo a facile N,N′-transacylation to give the 3-(2-aminophenyl)-2-pyrrolidones 4 in the absence of oxygen, whereas in the presence of oxygen 3a was oxidized to kynurenine.     

Studies of divacancy in Si using positron lifetime measurement

The charge state dependence of positron lifetime and trapping at divacancy (V₂) in Si doped with phosphorus or boron has been studied after 15 McV electron irradiation up to a fluence of 8.0×10¹⁷ e/cm². The positron trapping cross sections for V ₂ ^2– , V ₂ ^– and V ₂ ⁰ at 300 K were about 6×10^–14, 3×10^–14 and 0.1–3×10^–14 cm², respectively. For V ₂ ⁺ , however, no positron trapping was observed. The marked difference in the cross sections comes from Coulomb interaction between the positron and the charged divacancy. The trapping rates for V ₂ ⁰ and V ₂ ^2– have been found to increase with decreasing temperature in the temperature range of 10–300 K. These results are well interpreted by a two-stage trapping model having shallow levels with energy of 9 meV (V ₂ ⁰ ) and 21 meV (V ₂ ^2– ). The appearance of a shallow level for V ₂ ⁰ can not be explained by a conventional Rydberg state model. The lifetime (290–300 ps) in V ₂ ⁰ is nearly constant in the temperature range from 10 to 300 K, while that in V ₂ ^2– increases from 260 ps at 10 K to 320 ps at 300 K. The lifetime (260 ps) in V ₂ ^2– is shorter than that in V ₂ ⁰ at low temperature, which is due to the excess electron density in V ₂ ^2– . At high temperature, however, the longer lifetime of V ₂ ^2– than that of V ₂ ⁰ is attributed to lattice relaxation around V ₂ ^2– .     

Parametric modelling of Poisson-Gaussian random matrix ensembles

We analyse a scheme of transition from the Poissonian statistics for quantum levels to the Gaussian one of random matrix ensembles in the framework of level dynamics discussed by Yukawa. We propose a means of connecting these two limiting statistics by showing a result that Yukawa's parameter / of the exponential family can be efficiently replaced by the ratio <E>/<Q> which reflects directly a degree of the eigenvalue correlations of each sample matrix in the ensemble. On this basis, we discuss a correspondence between the level statistics of a generic quantum system and its classical regular/chaotic dynamics in terms of the semiclassical power spectrum and its second moment formulated by Feingold-Peres and Prosen-Robnik. We also discuss some limiting proceduresN (infinite limit of the matrix dimension) pertinent to the Gaussian ensembles, and remark about the possibility offractional power law of Brody's type.     

Photoinduced electron-transfer systems consisting of electron-donating pyrenes or anthracenes and benzimidazolines for reductive transformation of carbonyl compounds

Photoinduced electron-transfer reactions of several ketone substrates were studied to evaluate the utilities of 1,6-bis(dimethylamino)pyrene (BDMAP), 1,6-dimethoxypyrene (DMP), 9,10-bis(dimethylamino)anthracene (BDMAA), and 9,10-dimethoxyanthracene (DMA) as electron-donating sensitizers cooperating with 2-aryl-1,3-dimethylbenzimidazolines. BDMAP and DMP generally led higher conversion of ketones and better yield of reduction products compared to BDMAA and DMA.     

Neighboring effect of thiol group in acyl transfer reaction on a polymer with a lipoic acid structure

Reductive S-monoacylation of lipoamide with some carboxylic acids and tri-n-butylphosphine was carried out in acetonitrile to obtain the corresponding S-monoacylated compounds in excellent yield. This method was applied to the preparation of S-monoacylated dihydrolipoyl polymer with a neighboring thiol group. The acyl transfer from the polymer to cyclohexylamine was enhanced as much as 64 times by adding silver perchlorate.     

Estimation of frequency- and time-dependence of polymer composite system by viscoelasticity in three dimensions

This paper is concerned with the comparison between mechanical properties of polymer composite system and those of each individual constituent. The comparison is mainly performed with respect to the viscoelastic Young's modulus and the relaxation Young's modulus. These mechanical constants may be obtained from the correspondence principle by applying the Laplace transform to the constitutive equation. The calculated results exhibit that the mechanical property of polymer composite system strongly depends on that of matrix with respect to frequency- and time-dependences. That is, as for the vibration and dynamic response in the steady state, the frequency-dependence of peak position about imaginary part of dynamic modulus of composite system is similar to that of matrix, while the magnitude of dynamic modulus depends on volume fraction of dispersed particles to total volume. As for the stress relaxation, the time-dependence of the relaxation Young's modulus of composite system resemble that of matrix each other, while the magnitude depends on the volume fraction of dispersed particles to total volume. This is due to the calculating condition that particle is assumed to be very rigid in comparison with matrix in this paper.     

Synthesis of sodium-polystyrenesulfonate-grafted nanoparticles by core-cross-linking of block copolymer micelles

Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (R_h=15-23 nm, where R_h represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The R_h of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis.