分子手性的温度效应：D-丙氨酸的变温X衍射和中子衍射研究

利用X衍射（300, 270, 250 K）和中子衍射（300, 260, 250, 240 K）研究D-氨酸单晶在静态的和动力学的变温过程中的结构特征以及考证Salam预言的由D到L构型转变的可能性. 实验发现丙氨酸晶体的空间群P212121对称性没有改变. 实验结果否定了构型相变的可能，但是发现在~250 K有一个微小的、连续的对称性破缺发生. 晶体分子振动产生的环电流模型可以用来解释D-和L-丙氨酸单晶直流磁化率和天然旋光角相反的现象， 与之相关的中子衍射数据进一步揭示了变温过程中αC－H(2), N－H(1), N－H(4), N－H(6) 键长的不同变化. 中子衍射还显示了质子移动所导致的动力学无序，来源于分子内氨基和羧基形成的氢键和分子间αC－H和氨基形成的氢键，从而产生的晶格扭曲和NH³⁺的扭转. 实验结果表明Salam预言相变不是传统意义的结构相变，而是由于温度效应导致了在相变点附近分子的宇称破缺能差（PVED）增大，然后通过氨基酸分子的隧道效应扩大了宇称破缺能差的影响，这一研究为生命现象中快速的均一手性形成提供了非线性机理的合理解释.     

Curing reaction characteristics and phase behaviors of biphenol type epoxy resins with phenol novolac resins

Diglycidyl ether of 4,4′-dihydroxybiphenol (BPDGE) is a liquid crystalline epoxy. The biphenyl epoxy (diglycidyl ether of 3,3′,5,5′-tetramethyl-4,4′-biphenyl, TMBPDGE) has found great applications in plastic encapsulated semiconductor packaging. Phenol novolac (PN) was used as curing agent. The reaction kinetics of BPDGE/PN and TMBPDGE/PN systems in the presence of triphenylphosphine (TPP) were characterized by an isoconversional method under dynamic conditions using differential scanning calorimetry (DSC) measurements. The results showed that the curing of epoxy resins involves different reaction stages and the values of activation energy are dependent on the degree of conversion. The effects of curing temperature on their phase structure have been investigated with polarized optical microscopy and Wide-angle X-ray diffraction. With proper curing process, BPDGE showed a nematic phase when cured with PN.     

Formulation–composition map of a lecithin-based emulsion

Formulation–composition map is an interesting tool to predict the nature of an emulsion, stability, viscosity and nevertheless to decide the mixing protocol of its ingredients. Information based on optimum formulation (environmental conditions at which the affinity of an emulsifier for oil and for aqueous phase is same), which is depicted through hydrophilic–lipophilic deviation (HLD) concept, is necessary to make a formulation–composition map of an emulsion. In order to apply this concept in food emulsions, it is necessary to determine characteristic constants of each component of the system, i.e. the aqueous phase, the oil phase and the emulsifier at equilibrium. In this work formulation–composition map of a sunflower oil–water–lecithin system, based on the knowledge of phase behavior of lecithin at equilibrium and emulsification, was made. The shape of inversion line on formulation–composition map was not the classical stair type rather an almost vertical inversion line at water-fraction (f_w) near 0.20 was observed. It was supposed to be linked to the viscosity of oil phase which was 50 times the viscosity of aqueous phase. Additionally, emulsions were of oil-in-water (O/W) type for f_w higher than 0.20, but their viscosity and the drop size behavior with respect to salt concentration as formulation variable did not show the existence of transitional inversion line on formulation–composition map. Such map in advance can certainly facilitate the guidelines for dynamic emulsification.     

Stereoselective synthesis of 4-hydroxy-2-phenylproline framework

Highly diastereoselective (>20:1) bromo-lactonization of N-sulfonyl-2-allyl-2-phenylglycine methyl ester (11) was observed. Successive treatment of the chiral lactone with MeONa gave the desired (2S,4R)-4-hydroxy-2-phenylproline derivative in high yield without erosion of the diastereoselectivity. The starting chiral non-racemic compound (5) was prepared from the racemic 2-phenylglycine using a classical kinetic resolution (crystallization), an asymmetric phase transfer alkylation, and an enzyme-catalyzed kinetic resolution.     

乳状液法制备憎液溶胶Ⅰ.BaCO_3均匀粒子的制备

均匀胶体粒子的形成，除与反应条件（反应物浓度、陈化时间和温度、介质种类等）有关外，反应体系的环境也影响最终产物的形态，《至结晶结构．气溶胶法和微乳液法正是利用微环境中的‘水池效应”；分别制备出球形亚微米和纳米级的均匀粒子［‘－‘］、这些方法与水解法和相转化法等方法比较，反应物浓度要大几个数量级，而反应时间却短很多，因而受到研究人员的关注．乳状液也能提供亚微米、微米及以上级的微环境，因此，可以应用O／W乳状液乳液中的聚合反应制备亲液的分散体系．然而，极少有关利用w／O乳状液制备僧液溶胶的报导问；最近…     

Phase Equilibria and Critical Curves of Binary Ammonia–Hydrocarbon Mixtures

Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described.     

甲基丙烯酸—磷脂酰乙醇甲基丙烯酰胺共聚物LB膜的研究

制备了不同摩尔比的甲基丙烯酸-磷脂酰乙醇甲基丙烯酰胺共聚物,研究了这种共聚物在水面的表面压力(π)-分子面积(A)曲线、共聚物制成的MOS LB膜的电容(C)-电压(V)特性及此LB膜的相变温度。     

High-pressure phase transition in LiBH4

The high-pressure phase transition from ambient pressure α-LiBH₄ to high-pressure β-LiBH₄ was observed by Raman spectroscopy and X-ray diffraction between 0.8 and 1.1 GPa. The phase boundary between these two phases was mapped over a large range of temperatures using thermal conductivity studies and differential thermal analysis. The structure of the high-pressure phase could not be identified due to small number of experimentally observed reflections, but it was shown that it is different from previously reported theoretical predictions.     

Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

The microenvironment in polymer solids with added plasticizers. An attempt to measure the size and distribution of free volume in poly(methyl methacrylate) solids

Various amounts of n-alkylbenzenes (C_n: C₆H₅-C_nH_2n+1 (n = 3-16)) were doped into poly(methyl methacrylate) (PMMA) films, and the emission and thermal properties of each film were measured in detail together with their solid-state ¹³C NMR spectra. The aim of the present work was to estimate the size distribution of free volume in amorphous regions of polymer solids heavily doped with plasticizers by using C_n as models of a plasticizer. The excimer fluorescence yields of C_n in PMMA were found to depend on both the amount of C_n and the length of the alkyl chains of C_n, although the fluorescence spectra of all of the C_ns in dilute fluid solution were almost the same. The quantitative analysis showed: (1) C_n with n ? 12 induces a phase separation in PMMA, in which almost all of the C_n molecules are in a separated phase, and thus they cannot penetrate regions in which PMMA chains are aggregated. This means that C_n with n ? 12 cannot enlarge the space between PMMA chains. (2) Smaller C_n (n < 11) can enter free volumes between PMMA chains that correspond to their molecular size, but they can enlarge them only to a limited extent. Thus, the amount by which plasticization can increase the free volume of PMMA is limited by the size of the dopant and the inherent free volume of the polymer matrix. (3) The efficiency of excimer formation was found to reveal the maximum amount of C_n that could fit in the free volume of PMMA. Thus our fluorescence measurements showed that PMMA solids that were plasticized to their limit had a free volume that was larger than the volume occupied by all the conformers of C₅ and smaller than the volume occupied by almost all the conformers of C₁₂. In conclusion, we were able to obtain information on plasticization and to demonstrate a method of monitoring microenvironments in polymer solids after they have been doped with plasticizers.