Effect of the addition of NH4F on anodic behaviors of DSA-type electrodes in H2SO4-(NH4)2SO4 solutions

The effect of NH₄F addition on the high-anodic behaviors of various DSA-type electrodes was investigated in a mixture of sulfuric acid and ammonium sulfate. The pronounced effect of NH₄ addition was observed on DSA-type Ti/RuO₂, Ti/IrO₂?TiO₂ electrodes, but not observed on the other electrodes studied. The close relationship was found between the increment of the electrode potential caused by the NH₄ addition and the quantity of F^? adsorbed on the electrode surface. The effect of NH₄F addition was considered to be resulted from the adsorption of F^? on the electrode surface, and the presence of adsorbed F^? was directly proved.     

Surface active N-acylglutamate: I. Preparation of long chain N-acylglutamic acid

Long chain N-acylglutamic acid was prepared in a high yield by a reaction of glutamic acid with fatty acid chloride in a mixed solvent of water and a water miscible organic solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran,t-butyl alcohol or cyclohexanone. In this reaction the composition of the mixed solvent influenced the yield of N-acylated glutamic acid and the best yield was obtained when the reaction was carried out in the mixed solvent comprising 30–60% v/v of the organic solvent. Long chain N-acylaspartic acid was also obtained in a high yield by the same method. As the other method to obtain N-lauroyl-D L-glutamic acid, it was examined that N-acyl-α-aminoglutarodinitrile which was obtained by a reaction of α-aminoglutarodinitrile with fatty acid chloride was hydrolyzed with an aqueous alkaline solution. The salts of long chain N-acylglutamic acid are known as the surface active agents that react mildly on the human skin.     

Charged ultrafiltration membrane for permeation of proteins

Polyacrylonitrile-g-poly(N,N-dimethylaminoethyl methacrylate) was synthesized photochemically and quaternized. The positively charged membranes made from the quaternized graftcopolymer showed high ultrafiltration rate for water by adding poly(vinyl alcohol) to casting solution and washing it out after the casting. In buffered saline solution, the permeability of the membranes was very small at pH below isoelectric point of albumin but increased markedly at higher pH. On the other hand, the permeability for γ-globulin was very small and did not show any pH dependence.     

The electrocatalytic activities of the Pd-doped MnO2 for the chlorine evolution reaction

The anodic evolution of chlorine on the massive β-MnO₂ doped with various amounts of Pd was investigated in acidic chloride solution. A second-order relation was found between the rate of the chlorine evolution reaction and the number of active Pd sites at the electrode surface. And it was confirmed that, in the relatively low doped electrodes, the active sites are more effectively dispersed on the surface with microscopic homogeneity. From the activation energies, it was also suggested that the reaction mechanism on the MnO₂ doped with relatively small amounts of Pd is somewhat different from that on the pure PdO electrode.     

Anodic polarization of aluminium in organic electrolytes

The polarization characteristics of aluminium anodes have been studied in various organic electrolytes containing aluminium chloride. The small amount of oxide present on the metal was dissolved by an anodic pre-treatment. The charge transfer number of the overall reaction was three. The current density supported by the electrolytes decreased in the order nitromethane>acetonitrile >propylene carbonate, formamide>tetrahydrofuran. The rest potential increased in the order formamide     

Pyrolysis–molecular weight chromatography–vapor-phase infrared spectrophotometry: An on-line system for analysis of polymers. IV. Influence of cis/trans ratio on the thermal degradation of 1,4-polybutadienes

The influence of the cis/trans ratio of 1,4-polybutadienes on the volatile products formed during temperature-programmed thermal degradation to 15% weight loss has been investigated using a mass chromatograph (a gas chromatograph which directly provides mass numbers of resolved components of a mixture) and an “on the fly” vapor-phase infrared spectrophotometer. In order of amounts, major volatile products were 4-vinyl-1-cyclohexene (dimer), 1,3-butadiene (monomer), cyclopentene, and 1,3-cyclohexadiene. With increasing trans content, the relative quantities of 4-vinyl-1-cyclohexene decreased strongly, cyclopentene increased strongly, 1,3-butadiene decreased moderately, and 1,3-cyclohexadiene increased moderately. For a high-trans polybutadiene, increasing the heating rate produced relatively more monomer and dimer but less cyclopentene. Mass chromatograms from 1,4-polybutadienes which had been heated to 15% weight loss in their prehistory were similar to those obtained from 1,2-polybutadiene, indicating that 1,4-polybutadiene undergoes isomerization prior to degradation. Mechanisms for the formation of the main volatile products of decomposition are discussed.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Cholesteryl ester compounds containing alkyl branched acyl groups — their preparations,properties and applications

Cholesterol having a reactive hydroxyl group at C₃-position can react with fatty acids to give the corresponding cholesteryl esters. Most of the natural cholesteryl esters consist of straight alkyl chain fatty acids with a high melting point. In oleochemistry it is well known that alkyl branched fatty acids, which are derived from petroleum or the fat and oil industry, have low melting points (mp.) and are chemically more stable if they are saturated acids. We designed alkyl branched fatty acid cholesteryl esters by means of common esterification and found some esters having a low mp. (mostly as a liquid). They had no irritative effect on both animal and human skin. They showed characteristic emulsification properties, namely the formation of either O/W or W/O emulsion coexistence together with other lipid components. Applying them onto human skin, they were able to penetrate towards the stratum corneum and improve the water-retaining ability and the barrier function of the stratum corneum. Based on these properties we have been applying the alkyl branched fatty acid cholesteryl ester, especially the methyl branched isostearic acid cholesteryl ester (IS-CE), to a shampoo and a rinse as hair cosmetics, skin care cosmetics and bath-additive products in the past decade.     

Striped‐pattern deterioration and morphological analysis of injection moldings comprising polypropylene/ethylene α‐olefin rubber blends. I. Influence of ultraviolet irradiation

Unique deterioration with a periodical striped pattern on the injection moldings of polypropylene/rubber blends is reported. After exposure to ultraviolet irradiation with a sunshine fade meter, striped patterns appeared on the injection moldings along the flow direction of the molten resin during the filling process of injection molding, even though the initial specimen showed no sign of any stripe pattern on its surface. The stripe was carefully observed with ultrasonic echo imaging, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. As a result, a number of microvoids were observed inside the injected body at a depth of 50–100 μm from the surface. It became clear that the difference in the number of voids along the flow direction formed the stripe pattern. Surprisingly, these voids occurred in domains comprising a rubber phase. The distribution of voids in depth indicated the existence of a trace of a snakelike flow caused inside the injected body during the injection‐molding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Triterpene alcohols and sterols of Spanish olive oil

Nine Spanish olive oils, including three each of virgin (pressed oil), refined virgin, and B-residue (solvent-extracted pomace oil) oils from different commercial sources, have been analyzed for their unsaponifiable matter (USM). Four sterolic fractions separated from the oils have been analyzed by preparative thin-layer chromatography (TLC); these fractions are triterpene alcohols, 4-methylsterols, sterols and triterpene dialcohols. The compositions of the four sterolic fractions were determined as their acetates by gas-liquid chromatography (GLC) on an OV-17 glass capillary column. Identification of each component was carried out by argentation TLC, GLC and combined gas chromatography-mass spectrometry (GC-MS); 44 components were identified, of which four: 24-methylene-31-nor-9(11)-lanostenol, 24-methyl-31-nor-E-23-dehydrocycloartanol, 24-ethyl-E-23-dehydrolophenol and 5,E-23-stigmastadienol, were considered to be new sterols from natural sources. Several characteristics, including the content of triteterpene dialcohols in the USM and that of C-24(28) unsaturated sterols in each of the four sterolic fractions, which can be used to distinguish between virgin and B-residue olive oils, were observed.