Studies on relationship between activity and electron density on carbonyl oxygen in sex pheromone mimics of the American cockroach,part XI

From the relationship between structures of the 2-substituents of verbanyl analogs and their sex pheromone activities to the American cockroach, electron density of the carbonyl oxygen atom in the substituent, as estimated by the [¹⁷O]NMR chemical shift, was estimated to be an important factor which influenced the activity, in addition to length of the substituent and the position of the carbonyl group. (+)-Verbanyl methylcarbonate (XX), possessing the highest electron density on the carbonyl oxygen atom, showed the strongest activity among the analogs.For Part X, see Manabe et al., 1983. J. Chem. Ecol. 9:533–549.     

Mie scattering from sphere structures in polymer blends

Polymer blends of transparent poly(methyl methacrylate) and polystyrene become opaque due to light scattering at the boundaries of the two polymers. The polymer blend is light brown when it is illuminated by white light. The coloring depends on the spherical domain structures existing in the polymer blend. The coloring was analyzed by using the rigorous Mie theory. The Mie results were compared with the semiempirical results previously reported by the authors. The wavelength dependence of theoretical scattering efficiencies on radii of scattering spheres from 0.05 to 1.2 μm was obtained for polystyrene spheres in poly(methyl methacrylate) matrix, and vice versa. The scattering at the short wavelength region is stronger than at the long wavelength region. The scattering efficiencies become almost constant in the visible wavelength region for sufficiently large spheres.     

The surface film formed on amorphous Pd-Ti-P alloy by anodic polarization in 2 m NaCl solution

X-ray photoelectron spectroscopy was used to investigate the effect of the composition and thickness of surface film on the electrocatalytic properties for chlorine gas evolution on amorphous Pd-Ti-P alloy in NaCl solution. The amount of charge for gas evolution exhibited a wavy change with an increase in polarization potential. The gas evolution became active with an increase in palladium content of the surface film and slowed down with increases of titanium and phosphorus contents of the film. However, despite the fact that the formation of surface film consisting mainly of titanium as a cation in the potential region higher than 1.6 V (sce), the catalytic activity for gas evolution increased, suggesting the change in the gas evolution mechanism in the higher potential region.     

An X-ray photoelectron spectroscopic study of electrocatalytic activity of platinum group metals for chlorine evolution

A correlation of the catalytic activity for anodic chlorine evolution of platinum group metals to the nature of the surface film formed during chlorine evolution in a sodium chloride solution was studied by X-ray photoelectron spectroscopy. The change in the surface film with increasing potential was found on platinum, including an increase in the cationic valence. This seemed responsible for the decrease in the activity for chlorine evolution on platinum in the high potential region. Increasing potential did not result in the appreciable increase in the cationic valence in the surface film on the other platinum group metals. Replacement of hydroxyl ions in the surface film by chloride ions became easier in the order of rhodium, iridium and palladium, and the activity for anodic chlorine evolution increased in this order due possibly to an increase in the amount of chloride ions in the film which seemed to be one of the reactants in the rate determining electrochemical desorption of adsorbed chlorine atom. Chlorine molecules adsorbed on the surface film were also found. It was assumed that the activity for anodic chlorine evolution might be low when the metal surface was covered by a large amount of molecular chlorine which was the reaction product.     

Recognition of substrates by membrane potential of immobilized glucose oxidase membranes

The shifts in membrane potential, caused by the injection of glucose into a permeation cell, were measured using immobilized (entrapped) glucose oxidase membranes. No, pH change in the permeation cell was observed upon injection of glucose, but the shift in membrane potential was definitely detected. The shift in membrane potential was observed under nitrogen bubbling (in the absence of oxygen) using initially used enzyme membranes. It was, therefore, suggested that the shifts in membrane potential were not caused by an enzyme-substrate reaction, but by binding of the substrate to the enzyme, which indues a conformational change in the enzyme and leads to a change in charge density in the enzyme membrane. This mechanism is also supported by the fact that the shifts in membrane potential were observed upon injection of not only D-glucose but also L-glucose as reported in our previous study [J. Chem. Soc. Faraday Trans., 87 , 695 (1991)]. © 1994 John Wiley & Sons, Inc.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

Preparation of plasma-polymerized membranes from I-(trimethylsilyl)-I-propyne and gas permeability through the membranes

Summary Plasma-polymerized membranes for gas separation were prepared from 1-(trimethylsilyl)-1-propyne. The permeation data of He, H₂ 0₂, N₂, CO₂, and CH₄ through the membranes showed plasma-polymerized 1-(trimethylsilyl)-1-propyne had high permselectivity but low permeability compared with poly[l-(trimethylsilyl)-1-propyne]. This behavior is considered to be due to the crosslinking structure of the plasma-polymerized membrane. The correlation between plasma polymerization conditions and the membrane performance was studied. The optimum condition at which the deposition rate of the plasma polymer is maximized agreed with the optimum value to yield maximum separation factor of gases through the membrane.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Synthesis and properties of novel side-chain-sulfonated polyimides from bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone

A novel side-chain-sulfonated aromatic diamine of bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone (BAPSBPS) was synthesized. Sulfonated copolyimides were synthesized by random and sequenced block copolymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, BAPSBPS and nonsulfonated diamine. They displayed good solubility in common aprotic solvents and high desulfonation temperature of 350 °C, suggesting the high stability of sulfonic acid groups. The reduced viscosity was in the range of 0.4-1.8 dl/g at 0.5 g/dl and 35 °C. Flexible and tough membranes with reasonably high mechanical strength were prepared. They showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity (σ), taking their lower ion exchanging capacity (IEC) into account. For example, the membrane with IEC of 1.54 mequiv/g showed σ values of 81 and 11 mS/cm in water and 70% RH, respectively, at 60 °C.     

Anodic characteristics of amorphous ternary palladium-phosphorus alloys containing ruthenium,rhodium, iridium,or platinum in a hot concentrated sodium chloride solution

Amorphous ternary palladium-based alloys containing platinum group metals as an additional element were prepared by rapid quenching from the molten state and their anodic characteristics were investigated in a 4 mol dm^?3 NaCl solution of pH 4 and 80° C. The amorphous alloys containing sufficient quantities of rhodium, platinum or iridium were passivated by anodic polarization and their corrosion rates at high current densities in the chlorine evolution region were extremely low. This fact was attributed to the formation of a highly protective passive film due to both the transformation to the amorphous structure and the addition of rhodium, platinum or indium. The electrocatalytic activities for chlorine evolution of amorphous alloys were higher than those of pure platinum group metals except palladium. In particular, the amorphous Pd₄₁Ir₄₀P₁₉ alloy had the desired stable, high electrocatalytic activity for chlorine evolution and the high overvoltage for oxygen evolution.