The absolute configuration of (+)-oxopropaline D by theoretical calculation of specific rotation and asymmetric synthesis

The specific optical rotations of (R)-oxopropaline D calculated by two ab initio MO methods were +52+/-31 degrees and +61+/-29 degrees, respectively, and (+)-oxopropaline D (3) was presumed to have an R-configuration. On the basis of this theoretical result, the reaction of 1-litio-beta-carboline with (R)-glyceraldehyde acetonide followed by oxidation with MnO(2) gave (R)-oxopropaline D acetonide (4a), which was consistent with the previously synthesized (+)-oxopropaline D acetonide (4) in all respects. From the results of theoretical calculations and the experimental synthesis, we determined that natural (+)-oxopropaline D (3) has an R-configuration.     

Thermal diffusivity measurement of low-k dielectric thin film by temperature wave analysis

Thermal diffusivity of thin film with low dielectric constant (k), what is called low-k dielectric thin film, 0.31-1.14 μm, including hydrogen-silsesquioxane (HSQ), methyl-silsesquioxane (MSQ), and poly(arylen ether) was examined by temperature wave analysis. The phase shift of temperature wave was observable up to 100 kHz. Thermal diffusivity of HSQ was 4.7 × 10⁻⁷ m² s⁻¹, on the other hand it was not higher than 1.1 × 10⁻⁷ m² s⁻¹ for MSQ or poly(arylen ether) at room temperature. Temperature dependence of thermal diffusivity/thermal conductivity of MSQ was obtained, thermal diffusivity decreased but thermal conductivity increased in a heating scan at 30-150 °C. It was shown that the thermal diffusivity of low-k thin film was correlated with the chemical and the physical structures, the latter was formed in the spin-coating and the curing process.     

Measurement of diffusion coefficients of parabens and steroids in water and 1-octanol

Diffusion coefficients (D) of parabens and steroids in water and 1-octanol were determined by using the chromatographic broadening method at 37 degrees C, and the relationships between the D values and the physicochemical properties of the drugs were discussed. The D values in 1-octanol were lower than those in water because of the higher viscosity of 1-octanol. The D values depend on not only the molecular weight (MW), but also the lipophilicity of the drugs in water and on the ability for hydrogen-bonding in 1-octanol. When the lipophilic index (LI), calculated from the retention time using in a reverse-phase column, was used as a parameter of drug lipophilicity, the following equation was obtained for D in water (D(w)); log D(w)=-0.215.log MW-0.077.log LI-4.367. When the hydrogen bond index (HI), the logarithm of the ratio of the partition coefficient of the drugs in 1-octanol and cyclohexane, was used as an index of hydrogen-bonding, the following equation was obtained for D in 1-octanol (D(o)); log D(o)=-0.690.log MW-0.074.log HI-4.085.     

Capillary electrophoresis of anthraquinones from Cassia siamea

The separation and determination of two anthraquinones, emodin and chrysophanol, and two bianthraquinones, cassiamin A and cassiamin B, were achieved by capillary electrophoresis (CE). The running electrolyte used in this method was 0.05 M hydroxypropyl-gamma-cyclodextrin in 0.1 M borate buffer (pH 9) containing 10% acetonitrile, with an applied voltage of 20 kV. Application of this technique in the determination of the main bianthraquinones, cassiamin A and cassiamin B, of Cassia siamea is demonstrated in this paper.     

Oxidation of glucose to gluconic acid by glucose oxidase in a membrane bioreactor

Glucose oxidase (GO) (EC 1.1.3.4) was used as catalyst for oxidizing glucose into gluconic acid utilizing a 10-mL Bioengineering Enzyme Membrane Reactor® or a 400-mL Millipore Stirred Ultrafiltration Cell (MSUC) coupled with a Millipore UF membrane (cutoff of 100 kDa) and operated for 12 h under an agitation of 100 rpm, pH 5.5, and 30°C. The effect of feeding rate (0.10, 0.15, or 0.20 min^?1), glucose (2.5 or 5.0 mM), and GO (1.0 or 2.0 mg/mL) concentrations on the catalysis were studied. A yield of about 75% was attained when the MSUC filled with 1.0 mg/mL of GO was fed with 2.5 mM glucose solution at a rate of 0.15 min^?1.     

POSSIBLE ROLE OF METALLOTHIONEIN IN THE CELLULARDEFENSE MECHANISM AGAINST UVB IRRADIATION IN NEONATAL HUMAN SKIN FIBROBLASTS

Abstract –The role of metallothionein (MT) in protecting skin cells against UVB irradiation was investigated. Fibroblast strains from normal adult (HS-K) and neonatal (NB1RGB) human skins as well as keratinocyte strains from human skin (SV40-HSK) and newborn Balb/c mouse skin (Pam 212) were exposed to UVB irradiation.
The sensitivity of HS-K and NB1RGB cells to UVB irradiation was similar; those of SV40-HSK and Pam 212 cells were two- and six-fold as sensitive to UVB irradiation as HS-K cells, respectively. The HS-K cells contained the greatest cellular reduced form of glutathione (GSH) levels compared to the three other skin cells: the levels were 13-, 7- and 6-fold of those in NB1RGB, SV40-HSK and Pam 212 cells, respectively. These results indicated that the sensitivity of skin cells to UVB irradiation was not always associated with their endogenous GSH levels. In particular, despite the fact that NB1 RGB cells contained a relatively small amount of GSH, they were less sensitive to UVB irradiation.
NB1RGB cells contained 4–30 times more MT than those in other skin cells examined. The sulfhydryl residues of MT molecules in the NB1RGB cells were estimated to be mostly unoccupied by metals, suggesting they act in a similar way to those of GSH. Moreover, NB1RGB cells in which the MT content was elevated by dexamethasone (1 μg/mL ) or Zn²⁺ (7 μg/mL) treatment were more resistant to UVB irradiation than nontreated ones.
These results suggest that, at least in neonatal human skin fibroblasts, MT may play a role in protection against UVB irradiation.     

Capillary electrophoresis for simultaneous determination of emodin,chrysophanol, and their 8-beta-D-glucosides

The simultaneous separation and determination of the major anthraquinones, emodin, chrysophanol, and their glucosides, of Rumex japonicus HOUTT., and emodin and emodin glucoside, of Cassia tora L., Rhamnus purshiana DC., Polygonum multiflorum THUNB., and P. cuspidatum SIEB. et ZUCC., were achieved by cyclodextrin modified capillary zone electrophoresis. The running electrolyte used in this method was 0.005 M alpha-cyclodextrin in 0.03 M borate buffer (pH 10.5) containing 10% acetonitrile, with an applied voltage of 20 kV.     

Preparation of the thermotropic copoly(amide ester) of p‐aminobenzoic acid and m‐hydroxybenzoic acid with diphenyl chlorophosphate/pyridine

A thermotropic copoly(amide ester) exhibiting a nematic mesophase within the range of 240–360 °C was prepared by the solution copolycondensation of p‐aminobenzoic acid (40–70 mol %) and m‐hydroxybenzoic acid with diphenyl chlorophosphate in pyridine in the presence of LiCl. For control of the sequence distribution of p‐aminobenzoic acid, the amount of LiCl and the dropwise addition of the phosphate were examined. The transition temperatures (from a solid phase to a nematic mesophase) of the resultant copolymers were affected by the period of addition and the amounts of the aminobenzoic acid and LiCl and were investigated in terms of the distributions of the monomers determined by ¹H NMR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1775–1780, 2002     

5-Exo versus 6-endo cyclization of nucleoside 2-sila-5-hexenyl radicals: reaction of 6-(bromomethyl)dimethylsilyl 1',2'-unsaturated uridines

The mode of cyclization of 2-sila-5-hexen-1-yl radicals generated from 6-(bromomethyl)dimethylsilyl-1',2'-unsaturated uridines was investigated. In contrast to the case of the 2'-unsubstituted 6-silicon-tethered substrate (4), which undergoes exclusive 6-endo-cyclization, reactions of the 2'-substituted (Me, CO2Me, OBz, and Cl) derivatives (14, 20, 22, and 24) uniformly proceeded in preferential or exclusive 5-exo-mode. The Tamao oxidation of the resulting cyclized products was also carried out to synthesize the corresponding 1'-C-hydroxymethyl derivatives.     

Detailed process of adsorption of alkanes and alkenes on zeolites

The adsorption of alkanes and alkenes on zeolites is investigated by comparing the adsorption characteristics for three types of zeolite: ferrierite, ZSM-5, and mordenite. The activation energy for the diffusion of propane and n-butane on ferrierite and the heat of adsorption of C(2)-C(4) alkanes and alkenes on zeolites and silica are estimated based on Fourier transform infrared spectroscopy, and the diffusion processes in the micropores are elucidated by comparing the results with previously reported activation energies for n-butene diffusion. The adsorption of 1-butene on mordenite is also examined. The structure and process of experimentally observable adsorption is found to differ depending on the type of zeolite and adsorbing molecule, reflecting differences in the sizes of molecules and pores. This differing behavior is utilized to interpret the elementary adsorption processes of alkanes and alkenes on zeolites.