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.     

Structure and Nonlinear Optical Properties of Lanthanide Borate Glasses

The third–order nonlinear optical susceptibility, χ⁽³⁾, of lanthanide (lanthanum, praseodymium, neodymium, and samarium) borate glasses has been measured by the third harmonic generation method. The structure of the present glass system has been studied by infrared and Raman spectroscopic methods. The network structures of the present Ln₂O₃–B₂O₃ glasses have been confirmed to be basically similar to each other. Praseodymium, neodymium, and samarium borate glasses exhibit χ⁽³⁾ values that are larger than lanthanum borate glasses, because of the optical resonance effect, in accordance with the f – f transition. Especially, the χ⁽³⁾ value for 30Pr₂O₃·70B₂O₃ glass is 1.8 × 10⁻¹² esu, which is a factor of ∼60 larger than that of SiO₂ glass. This striking enhancement of χ⁽³⁾ is mainly attributed to the large transition moment to the first excitation state.     

Interaction of cation-exchange membrane with polycation I. Poly(N-methyl-4-vinylpyridinium chloride)

We elucidated the effect of the molecular weight of poly(N-methyl-4-vinylpyridinium chloride) (PMVP) on its adsorbed or ion-exchanged amount on the cation-exchange membrane and the preferntial permselectivity of the membrane for sodium ion to calcium ion. The amount of the adsorbed or ion-exchanged PMVP increases with time and then attains to a definite value at a definite concentration. Also, the ultimate value increases with increasing the concentration of PMVP. When the molecular weight of PMVP is 3090, the ratio of the pyridinium groups of PMVP ion-exchanged with the sulfonic acid groups on the membrane surface to the total pyridinium groups of the cohered PMVP is in the range of 70–80%. The relative transport number of calcium ions to sodium ions(P_Na^Ca) decreases with increasing the amount of adsorbed or ion-exchanged PMVP and the numbe rof non-ion-exchanged pyridinium groups of PMVP and the number of non-ion-exchanged pyridinium groups of PMVP on the membrane surface. The smaller the molecular weight of PMVP, the more the adsorbed or ion-exchanged amount and the more preferable the permselectivity for sodium ion.     

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.     

Sterols ofKalanchoe pinnata: First report of the isolation of both C-24 epimers of 24-alkyl-Δ25-sterols from a higher plant

Eighteen sterols were isolated from the aerial parts ofKalanchoe pinnata (Crassulaceae) including four novel sterols,viz. (24R)-stigmasta-5,25-dien-3β-ol (24-epiclerosterol), (24R)-5α-stigmasta-7,25-dien-3β-ol, 5α-stigmast-24-en-3β-ol, and 25-methyl-5α-ergost-24(28)-en-3β-ol. 24-Epiclerosterol and its Δ⁷-analog occur together with their 24S/β-epimers in the same plant making this the first report of the isolation of both C-24 epimers of Δ²⁵-unsaturated 24-alkylsterols from a non-marine organism. Iodine-catalyzed isomerization of stigmasta-5,24-dien-3β-ol (24-ethyldesmosterol), the main sterol ofK. pinnata, yielded 24-epiclerosterol among other products.     

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.