Syntheses of amphiphilic block copolymers by living cationic polymerization of vinyl ethers and their selective solvent‐induced physical gelation

Amphiphilic diblock copolymers were prepared by the living cationic polymerization of vinyl ethers in the presence of added bases, and their selective solvent‐induced physical gelation behavior was investigated. The block copolymerization of 2‐phenoxyethyl vinyl ether (PhOVE) and 2‐methoxyethyl vinyl ether (MOVE) was carried out in the presence of ethyl acetate with Et_1.5AlCl_1.5 in toluene at 0 °C. Despite the rate difference, diblock copolymers with a very narrow molecular weight distribution were obtained, quantitatively. By adding the selective solvent, water, to the acetone solution of the diblock copolymer, PhOVE₂₀₀‐b‐MOVE₄₀₀, physical gelation occurred suddenly and the system ceased to flow, maintaining transparency. Viscoelastic measurements and transmission electron microscopic observations were performed to examine the characteristic gelation behavior and structure of the obtained gels. Various gelation conditions and physical gelation by other amphiphilic block copolymers were also designed on the basis of the solubility of each block segment. Further, new forms of physical gelation, accompanied by the solubilization of immiscible organic compounds, were achieved using similar diblock copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3190–3197, 2001     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.     

Synthesis of ion-exchange membranes by radiation-induced multiple grafting of methyl α,β,β-trifluoroacrylate

Methyl α,β,β-trifluoroacrylate (MTFA) was grafted onto polymer films with the multiple grafting technique initiated by α-rays: the yields were similar to those of the single-step grafting procedure with any irradiation dose. Grafted polymer obtained in the single-step experiments were distributed mainly near the film surface, whereas graft polymer from the multiple grafting experiments were distributed uniformly in the film at graft yields greater than 20%. The electric resistance of the hydrolyzed multiple graft polymer film in a 2N NaOH solution was much lower than that of one-step graft film at the same graft yield.     

A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene

Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH₄ → CH₄ + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH₄, which is a local model of the sp³ defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp³ defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials.     

Values in Japanese mathematics education: their historical development

Individual mathematics teachers may value different aspects of teaching and learning mathematics, but at the same time their value systems are under the influence of socially shared values. This paper describes such values in Japanese mathematics education from a historical and normative perspective. After the introduction of Western mathematics into the modern school system in the Meiji period (1868?C1912), the people of Japan struggled to adapt and absorb it onto the foundation of Japanese tradition. In the subsequent development of Japanese mathematics education, the integration of both practical and theoretical aspects have been issues, alongside changes in educational focus and in society at large, which are symbolically represented by the enrolment rates at all of elementary, secondary, and tertiary education levels. Mathematics education in Japan has also been subject to international influences, such as the reform movement and the modernization movement, at critical junctures in its development. Key concepts such as mathematical ideas, mathematical thinking, and mathematical activities are traces of such historical efforts by the Japanese mathematics education community, and represent their socially shared values.     

Generic cryptographic weakness of k-normal Boolean functions in certain stream ciphers and cryptanalysis of grain-128

This paper considers security implications of k-normal Boolean functions when they are employed in certain stream ciphers. A generic algorithm is proposed for cryptanalysis of the considered class of stream ciphers based on a security weakness of k-normal Boolean functions. The proposed algorithm yields a framework for mounting cryptanalysis against particular stream ciphers within the considered class. Also, the proposed algorithm for cryptanalysis implies certain design guidelines for avoiding certain weak stream cipher constructions. A particular objective of this paper is security evaluation of stream cipher Grain-128 employing the developed generic algorithm. Contrary to the best known attacks against Grain-128 which provide complexity of a secret key recovery lower than exhaustive search only over a subset of secret keys which is just a fraction (up to 5%) of all possible secret keys, the cryptanalysis proposed in this paper provides significantly lower complexity than exhaustive search for any secret key. The proposed approach for cryptanalysis primarily depends on the order of normality of the employed Boolean function in Grain-128. Accordingly, in addition to the security evaluation insights of Grain-128, the results of this paper are also an evidence of the cryptographic significance of the normality criteria of Boolean functions.     

Stackelberg solutions for fuzzy random two-level linear programming through level sets and fractile criterion optimization

This paper considers Stackelberg solutions for two-level linear programming problems under fuzzy random environments. To deal with the formulated fuzzy random two-level linear programming problem, an α-stochastic two-level linear programming problem is defined through the introduction of α-level sets of fuzzy random variables. Taking into account vagueness of judgments of decision makers, fuzzy goals are introduced and the α-stochastic two-level linear programming problem is transformed into the problem to maximize the satisfaction degree for each fuzzy goal. Through fractile criterion optimization in stochastic programming, the transformed stochastic two-level programming problem can be reduced to a deterministic two-level programming problem. An extended concept of Stackelberg solution is introduced and a numerical example is provided to illustrate the proposed method.     

α-Carboxylation reaction of carbonyl compounds with bromomagnesium ureide-carbon dioxide adducts

Bromomagnesium ureide-carbon dioxide adducts, models of the carboxylated biotin complex, undergo caboxylation of a variety of carbonyl compounds in good yield.