Structure formation and dynamics of water in strong external electric fields

We have performed molecular dynamics computer simulations of water in homogeneous external electric fields which were varied in a wide range of field strengths. The dielectric response is found to be linear up to fields E₀≈0.01 V/Å from where dielectric saturation effects become important. At fields of E₀≈3 V/Å a phase transition into an ordered, ice-like structure is observed, which is stabilized through hydrogen-bonds. With an increasing external electric field, the frequency spectrum of the water dynamics shows a remarkable red shift of the intramolecular modes and a blue shift of the librational motions, where the frequency varies quadratically with the field strength. A simple analytical model is discussed which reproduces the observed behavior.     

Controlled phase separations in solutions of soluble polyelectrolyte complex of DIVEMA (copolymer of divinyl ether and maleic anhydride)

Copolymer of divinyl ether and maleic anhydride (DIVEMA) is known to possess some anti-tumor and immune-stimulating activity and use as a drug carrier in anti-tumor drug delivery systems. Samples of DIVEMA of different degrees of polymerization were synthesized and characterized. Interaction of the hydrolyzed water-soluble DIVEMA polyanions with poly(N-ethyl-4-vinylpyridinium) cations (PEVP) has been studied. According to the potentiometry data, almost all carboxylic groups of the polyanions were able to form ion pairs with PEVP. In aqueous and water-salt solutions, formation of either soluble or insoluble polyelectrolyte complexes occurred depending on pH, ratio of the oppositely charged groups, and degree of polymerization of PEVP and/or DIVEMA. The phase separations followed general rules revealed by studying mixtures of PEVP and polycarboxylic acids. However in the case of DIVEMA, a significant broadening of the region for insoluble complexes at the expense of the region of soluble complexes was established. The data obtained demonstrate plausible advantages of the complex formation as the non-covalent modification of the polymeric carrier that endow DIVEMA with the ability for reversible soluble-insoluble transformation, in particular at physiological pH and ionic strength.     

填料对聚合物共混物相分离行为的影响

近年来,由于粒子填充聚合物共混物的广泛运用,复合材料的结构研究具有重要意义.除了研究粒子在聚合物中的分散外,关于粒子对聚合物共混物的相分离影响也做了大量工作.研究结果表明粒子的尺寸,粒子的表面处理以及粒子含量对聚合物共混物相分离热力学以及动力学有重要影响.由于粒子对聚合物组分的选择吸附、聚合物分子对粒子的润湿作用、填料对聚合物相区生长的阻碍导致了聚合物共混物-填料体系相行为的复杂性.本文扼要地综述了聚合物共混物-填料体系相分离的理论基础以及实验结果,介绍了粒子对相分离的影响因素,并展望了该领域的研究趋势和前景.     

The ordered phase of methylammonium lead chloride CH3ND3PbCl3

The perovskite-structured compound methylammonium lead chloride orders into a low-temperature phase of space group Pnma, in which at 80 K each of the orthorhombic axes , and is doubled with respect to the room temperature disordered cubic phase (). The structure was solved by ab initio methods using the programs EXPO and FOX. This unusual cell basis for space group Pnma is not that of a standard tilt system. This phase, in which the methylammonium ions, are ordered shows distorted octahedra. The octahedra possess a bond angle variance of 60.663°² and a quadratic elongation of 1.018, and are more distorted than those in the ordered phase of methylammonium lead bromide. There is also an alternating long and short Pb-Cl bond along a, due to an off-center displacement of Pb within the octahedron. This suggests that the most rigid unit is actually the methylammonium cation, rather than the PbCl₆ octahedra, in agreement with existing spectroscopic data.     

1─芳氧基乙酰基─4─苯甲酰氨基硫脲衍生物的合成及其生物活性研究

１─芳氧基乙酰基─４─苯甲酰氨基硫脲衍生物的合成及其生物活性研究魏太保，陈继畴（西北师范大学化学系，兰州，７３００７０）杨素铀，王秀春（西北师范大学生物系，兰州，７３００７０）关键词：１—芳氧基乙酰基—４—苯甲酰基氨基硫脲，相转移催化，合成，生物活性...     

Volume and heat capacity of model non-aqueous self-assembly systems

Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C₁₃E₆), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid

The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. −10° for Cd-PMA and ca. −15° for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.     

Theoretical study of cyclic conjugation in phenes: Some hitherto unnoticed features

Summary Cyclic conjugation in phenes is examined by means of theBosanac-Gutman-Aihara method. In contrast to the predictions based on the analysis ofKekulé orClar structures, we find that when going along the hexagons of a phene molecule, cyclic conjugation varies in a rather non-uniform manner. In contrast to a number of other homologous series of benzenoid hydrocarbons, the intensity of cyclic conjugation in phenes increases when going towards the center of the molecule.

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Theoretische Untersuchung der cyclischen Konjugation in Phenen: Einige bisher unbekannte Eigenschaften

Zusammenfassung Die cyclische Konjugation in Phenen wird mittels derBosanac-Gutman-Aihara-Methode untersucht. Im Gegensatz zu auf der Analyse vonKekulé- oderClar-Strukturen beruhenden Voraussagen variiert die cyclische Konjugation entlang der Sechsecke eines Phenmoleküls ziemlich unregelmäßig. Anders als bei anderen homologen benzenoiden Kohlenwasserstoffen nimmt bei Phenen die Intensität der cyclischen Konjugation zum Zentrum des Moleküls hin zu.

     

Phase separation behavior of epoxy resin modified with crosslinked rubber

Low molecular weight liquid rubber (ATBN = amine terminated butadiene acrylonitrile copolymer or CTBN = carboxyl terminated butadiene acrylonitrile copolymer)–DGEBA (diglycidyl ether of bisphenol A) blends indicated upper critical solution temperature (UCST) behavior. The phase separation behavior of the neat and crosslinked rubber (ATBN, CTBN)–epoxy blends was analyzed by a laser light scattering experiment. Lauryl peroxide (LPO) was employed to crosslink the rubber during the initial annealing stage. The onset point of the phase separation in the crosslinked ATBN–epoxy system occurred later than in the case of the neat ATBN–epoxy system. However, the onset point of the phase separation process started earlier in the case of the crosslinked CTBN–epoxy system. The domain correlation length of the crosslinked rubber-added system was smaller than that of the neat rubber-added system.     

高折光指数光学树脂的合成——相转移法合成不饱和硫醇酯单体的条件控制

采用正常的低温相转移催化（ＰＴＣ）和反滴碱溶液ＰＴＣ法分别合成了含硫双烯ＭＥＳＤＭＡ和单烯ＭＥＰＳＭＡ．１Ｈ ＮＭＲ分析证明ＭＥＳ中的杂质主要是由原料ＴＤＧ引入的．对含单个巯基的ＭＥＰＳ的正常ＰＴＣ酯化接枝双键，因存在巯基和不饱和双键的加成反应而导致失败．作者最终得到了折光指数在１６２５以上的ＭＥＳＤＭＡ／ＭＥＰＳＭＡ共聚物．