Phospholipases Induce Melanogenesis in Organ-Cultured Skin

Guinea pig skin becomes more pigmented following exposure to UV rays. This melanization was accompanied by enhanced intensity of tyrosinase-staining and increased number of tyrosinase-positive melanocytes (MEL^ty+), with resultant enhancement of melanin synthesis. To clarify the regulatory mechanism for melanization following UV irradiation, organ-cultured guinea pig skins have been used to examine their melanogenic responses to exogenous stimulation. This organ culture system responded well to UV irradiation, by increasing melanogenic activity. Also, in this system, phospholipases (PL), arachidonic acid, interleukin-1α and melanocytestimulating hormone, but not endothelin-1 or phosphatidylinositol-specific PLC (PI-PLC), stimulated melanogenesis to various extents as indicated by the number of MEL^ty+ and morphological changes. Among them, the PLA₂ and PLD were found to have a potent stimulatory property for melanocytes. They might affect melanocytes directly or indirectly through an effect on keratinocytes. These results suggest that PLA₂ and PLD play a key role in epidermal hyperpigmentation after UV irradiation or inflammation.     

Preparation of Saccharide-Silica Composites by a Sol-Gel Method and the Application for Optical Resolution of Metal Chelate Compounds

A novel organic-inorganic composite was prepared by a sol-gel process using hydrolysis and condensation of tetraethoxysilane (TEOS) reacted with a saccharide. During the process, ethoxy groups of the TEOS were replaced with hydroxyl groups of the saccharide and, consequently, saccharide molecules were combined with silica through their hydroxyl groups. Samples obtained under different reaction conditions were used for optical resolution of a metal chelate compound. The resolution ability of the composites was affected by the amount of water added for hydrolysis and of the saccharide. In particular, the amount of water drastically influenced the optical resolution performance. Composites obtained at the lower H2O/TEOS ratio gave the metal chelate compound a higher optical rotation. Three types of composites with the same composition were prepared by kneading, impregnation and by the sol-gel method, and were compared. The sol-gel composite showed the best optical resolution ability. It was concluded that the optical resolution ability was closely related to dispersibility of saccharide in the silica matrix.     

Cidep study of radical-ion pair systems: Photooxidation reactions of carbazoles by maleic anhydride in alcohol solution

Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems (methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles in thermal equilibrium.     

Broad spectrum and mode of action of an antibiotic produced byScytonema sp. TISTR 8208 in a seaweed-type bioreactor

A photobioreactor was constructed using anchored polyurethane foam strips (1 x 1 x 40 cm) fixed onto a stainless-steel ring to prevent flotation, as a biomass support material (BSM). This type of reactor was named a seaweed-type bioreactor. A filamentous cyanobacterium, Scytonema sp. TISTR 8208, which produces a novel cyclic dodecapeptide antibiotic, was immobilized in seaweed-type photobioreactor and cultivated with air containing 5% CO₂ sparged at a gas flow rate of 250 mL/min under illumination at a light intensity of 200 μmol photon m^-2s^-1. The antibiotic produced in the seaweed-type photobioreactor was purified by HPLC and examined regarding its spectrum and mode of action. The antibiotic effectively inhibited the growth of Gram-positive bacteria, pathogenic yeasts, and filamentous fungi, but it had only a weak effect on Gram-negative bacteria. Scanning electron micrograph analysis showed that the most characteristic change was swelling of the cells after exposure to the antibiotic. The antibiotic seems to alter the conformation of the microbial cell membrane, thereby changing its permeability, leading to osmotic shock.     

Osmotic coefficients of vinylic polyelectrolyte solutions without added salt

 The osmotic pressures of –polyelectrolyte solutions without added salt was measured in the concentration ranges 0.001–0.02 and 0.2–1.9 mol kg^-1. Our results show that the osmotic coefficients φ_p were strongly dependent on the chemical structures of polyelectrolyte through the polyion radius and the interaction between the ionic moiety and counterions. The osmotic pressures in polyelectrolyte solutions without added salt, calculated on the basis of the counterion contribution, are in agreement with the experimental results. We conclude that the counterion contribution is dominant in the osmotic pressures and thus, the polymer contribution is negligible in the examined concentration range 0.2–1.9 mol kg^-1. The P–B approach gave a fair prediction of the absolute values of the osmotic pressures with λ=4.5, where λ is the charge density parameter, except for NaPA. In other words, the concentration dependence of the φ_p values can be explained in terms of the counterion contribution. Received: 11 June 1997 Accepted: 19 August 1997     

Quantitative analysis of methylguanidine and guanidine in physiologic fluids by high-performance liquid chromatography-fluorescence detection method.

A rapid and sensitive high-performance liquid chromatographic method has been developed for the quantitative analysis of methylguanidine and guanidine in physiological fluids. These quanidino compounds are separated on a 6 x 0.23 cm cation-exchange column with 0.5 M sodium hydroxide solution. The guanidino compounds are detected with a fluorometer, which monitors the fluorescent guanidine derivatives produced by the reaction of the eluted constituents with 9,10-phenanthrenequinone. Sensitivity to sub-nanomole levels of methylguanidine and guanidine is demonstrated. The method was successfully applied to physiological fluids such as serum and cerebrospinal fluid from uremic patients.     

A facile access to α-phenylselenenyl carbonyl compounds by electrochemical oxidation

A novel α-phenylselenenylation of carbonyl compounds has been performed by electrolysis of a solution of ketones, diphenyl diselenide, tetraethylammonium bromide, and magnesium bromide in polar solvents (MeOH, AcOH, MeCN). The electrolysis enables us to prepare the desired seleno-carbonyl compounds without employing strong bases and the activated selenenyl reagents PhSeX.     

Chemical and biological modification of bleomycin,an antitumor antibiotic

Dedicated to Professor John C. Sheehan on the occasion of his sixty-fifth birthday. Chemical and biological modifications of bleomycin, an antitumor glycopeptide antibiotic, have been achieved by three procedures analogous to the modifications of penicillin.     

Raman spectra of anthracene negative ions in tetrahydrofuran solution

Raman spectra of anthracene mono- and di-negative ions in tetrahydrofuran solution were obtained by HeNe and Ar⁺ laser exciting lines. In addition to some frequency shifts from neutral anthracene, remarkable enhancement of intensities by the resonance Raman effect was observed for many aromatic ring vibrations.     

Elimination of the 4-hydroxyl group of the alkaloids related to morphine—I

Sinomenine, an alkaloid of the Japanese plant Sinomenium acutum, was converted to the 4-phenylether by the Ullmann reaction in a good yield. The Clemmensen reduction of sinomenine-phenylether and of its derivatives gave (+)-3-methoxy-4-phenoxy-N-methyl-Δ^x-morphinan.

Hydrogenation and successive sodium-liquid ammonia reduction of (+)-3-methoxy-4-phenoxy-N-methyl-Δ^x-morphinan gave (+)-3-methoxy-N-methylmorphinan.