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.     

Structure of a novel phytoecdysteroid,vitexirone, and efficient isolation of phytoecdysteroids fromVitex fisherii

A novel phytoecdysteroid, vitexirone, has been isolated from a MeOH extract of the root bark of the East African medicinal plantVitex fisherii by recycling high-performance liquid chromatography on a semipreparative scale. In addition, three known phytoecdysteroids, 20-hydroxyecdysone, ajugasterone C, and turkesterone, also were isolated. The structure of vitexirone has been established spectroscopically. The position and stereochemistry of the 11--hydroxy group of ajugasterone C and vitexirone were confirmed by the¹H-¹H homonuclear COSY NMR data. These phytoecdysteroids disrupt the molting process of the pink bollwormPectinophora gossypiella.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

Studies on ion-exchange membranes. XXXII. Heterogeneity in ion-exchange membranes

Twelve kinds of cation-exchange membranes were treated with hydrogen peroxide. Some of them (Selemion CMV, Nepton CR-61, Scrion C-100, SAM-1) were completely destroyed. Heterogeneity is believed to be present in that part of their chemical structures that is decomposable by the treatment. The other membranes were converted into porous membranes by the decomposition of the resinous part. Water permeabilities and electric resistances of the porous membranes were examined to evaluate the pore radius. It was concluded that the “paste method” membranes have a heterogeneity or localized distribution of the resinous part under 50 mμ. The “paste method” membranes seemed to resemble the “graft method” membranes in chemical structure and to be much different from the mosaic-type membranes such as Permaplex and MC-3142. These results were also supported by extraction of the membranes with appropriate solvents and observation by electron microscopy.     

In Situ Observation of Zirconia Particles at 1200°C by High-Resolution Electron Microscopy

Zirconia (ZrO₂) particles (average diameter, 30 nm) were observed in an in situ heating experiment up to 1200°C using a 400-kV high-resolution electron microscope. Thermal vibration of atoms on a (001) surface plane was observed at 1100°C. At 1200°C, grain growth and sintering phenomena were recorded on a videotape, showing (100) lattice planes migrating on a surface of a particle. Direct observation of the sintering process on a lattice level was accomplished for the first time.     

Reactions of phenols with tung oil

As regards the aromatic ring substitution reactions of various kinds of phenols with tung oil under acidic conditions, an investigation was made on the influences of the kinds and substitution positions of alkyl groups of the phenlos on the reaction. Alkyl phenols increased in reactivity in the order of ortho, meta, and para in the position of alkyl substitution. This can be attributed to the preferential para addition of tung oil to the phenol nucleus as reported in the previous paper. The larger alkyl group gave increased reactivities in the reactions of alkyl phenols with tung oil. This has something to do with compatibilities between phenols and tung oil (differences in solubility parameter between phenols and tung oil).     

Conformational studies of poly(N-methyl-l-alanine) by n.m.r. spectroscopy

Nuclear magnetic resonance (n.m.r.) and circular dichroism of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ in methylene $\text{chloride}\text{-d}{}_2\text{dichloroacetic acid}$ were investigated. In methylene chloride-d₂$\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was found to consist of nearly all-trans amide bonds and assume a stable secondary structure. Trace amounts of cis amide bonds were also present. The addition of dichloroacetic acid destroyed the secondary structure and induced a drastic change of the n.m.r. spectrum, which was similar to that observed with the monomeric amide, $\text{N-}\text{acetyl}\text{-N-}\text{methyl-}\text{l}\text{-alanine}$ dimethylamide. In comparison of the polymer with the monomeric amide, it was concluded that the transition of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was caused by the isomerization of amide bonds. The complex n.m.r. spectrum was interpreted in terms of the distribution along the polymer chain of various non-planar amide links as well as planar cis and trans amide links. The difference of the mechanism of conformational transition between poly(amino acid) and poly(imino acid) is also discussed.     

Negative emotion recognition using multimodal physiological signals for advanced driver assistance systems

Artificial Life and Robotics - Recent advanced driver assistance systems’ (ADASs) control cars to avoid accidents, but few of them consider driver’s comfort. To realize comfortable...     

A Possible Magnetic Phase with Scalar Chirality in Solid 3He Layers

We study quantum effects in a system of S = 1/2 spins with two–, three and four–spin exchange interactions on the triangular lattice, a possible model of the nuclear magnetism of solid ³ He layers. The ground state phases found in our previous work are studied by using the linear spin–wave theory. The uuud state shows a very flat spin–wave dispersion, which suggests that this state, though locally stable, will not survive non–linear quantum effects. The tetrahedral state, which has long–range order of a scalar chirality, is found to be stable against spin wave fluctuations. The ground state energies of different phases are compared. Results of numerical analysis of finite size clusters are also presented.