二组分平衡体系的T-x相图

主要从3个方面介绍了二组分平衡体系的T-x相图。一是简单相图的介绍;二是简单相图的组合;三是实际体系复杂相图的认识。从而可以让学生理解和掌握相平衡中的二组分体系的气-液、液-液和液-固平衡的T-x相图,并为实际应用打下良好的基础。     

二组分体系的相图及其相图边界理论

主要探讨了二组分体系的相图,如气-液相图和液-固相图,总结了二组分相图的分类、绘制及相图分析,这有利于理解和掌握二组分相图的基本规律。并简单介绍了相图边界理论,扩展了相图的热力学研究。     

MeX－REX_3系相图的模式识别分析

用化学键参数－模式识别或人工神经网络方法研究ＭｅＸ－ＲＥＸ_３型熔盐相图，总结中间化合物的形成、化学配比和Ｍｅ_３ＲＥＸ_６型化合物同分或异分熔化规律，并对其熔点或分解点进行预报．     

Phase Diagrams and Solubilization of Chlorocarbons in Chlorocarbon/Water/Anionic Surfactant/Alcohol Microemulsion Systems

The solubilization abilities of various chlorocarbons were investigated in a middle phase microemulsion system anionic surfactant sodium dodecyl sulfate (SDS) or sodium dodecyl sulfonate (AS)/n-butanol/chlorocarbon/brine with a ε-β fishlike phase diagram. The composition of the balanced interfacial layer of the microemulsion and some other parameters are calculated. The result shows that surfactant little dissolves in water and chlorocarbon phases, while alcohol mainly dissolves in water and oil phases besides in the interfacial layer. The order of the solubilization ability is dichloromethane (CH₂Cl₂) ～ carbon tetrachloride (CCl₄) > tetrachloroethylene (PCE) > o-dichloro-benzene. The solubility of the alcohol decreases with the increase in NaCl concentrations, which should be compensated by the increase in the amount of alcohol as cosolvent (Cs), so as to maintain the balanced interfacial layer. Salinity has little effect on the partition of surfactant between phases.     

CTAB/正丁醇-正辛烷-水和盐水的拟三元体系相图及微乳液微观结构的电导研究

绘制了CTAB/正丁醇-正辛烷-水和Al(NO₃)3(或Na2WO4)盐水拟三元体系的35℃相图.用电导法并结合电解质理论讨论了微乳液的微观结构,将整个微乳液单相区分为W/O微乳区、O/W微乳区和B.C.双连续区,并且用渗滤理论确定了一个分散相质点为W/O球状结构的反胶团微乳液区.     

用于固相萃取的聚乙二醇交联辛烷基、苯基、氨基和氰基固定相

用简单的方法合成了用于固相萃取的填料，填料含辛烷基，苯基，氨基或氰基及聚乙二醇链。这种固定相属于混合功能限进介质。其特点为表面有亲水性和一定程度的疏水性，只吸附少量蛋白质，蛋白质在4种固定相上的吸附量为0．98－3．62mg/g，苯基，氨基和氰基的聚乙二醇交联固定相在pH值4．5对蛋白质的吸附能力最大，而辛烷基聚乙二醇交联固定相在pH值2．5对蛋白质的吸附能力最大，固定相的塔板数能满足固相萃取的要求，含蛋白质的药物样品回收率为92％－115％，合成的固定相可用作生物样品的预处理。     

Phase Transition and Phase Transformation in Block Copolymer Nanoparticles

Block copolymer nanopaticles were prepared from the mixture solutions containing good/poor solvents by a simple evaporation process. The block copolymers formed disorder, unidirectionally stacked lamellar, and onion‐like structures in nanoparticles depending on preparation temperatures. Thermal annealing induced the disorder‐order phase transition and order‐order phase transformation in the block copolymer nanoparticles, even though the annealing temperature is lower than the of one polymer segment. The unusual thermal behaviors suggest that the glass transition temperature of the block copolymer is decreased by the effect of nanoparticle, whose surface areas are larger than their volumes.

     

Structural and Anion Coordination Features of Macrocyclic Polyammonium Cations in the Solid,Solution and Computational Phases

Abstract

The crystal structures of two hexaaza macrocycles 1,4,7,12,15,18-hexaazacyclodocosane ([22]N₆:1-6H⁺, 6C1^?) and 1,13-dioxa-4,7,10,16,19,22-hexaazacyclotetraeicosane ([24]N₆O₂:2-6H⁺,6CI^?) as their hexa-hydrochloride salts have been determined. 1-6H⁺ binds specifically two CI^? anions above and below the almost planar hexaammonium macrocycle yielding a dinuclear CI^? complex. The hexacation 2-6H⁺ on the other hand interacts preferentially with three CI^? anions of the six present in the solid state. Among the three closest anions, one of them, interacting with four ammonium groups, is located in the centre of the macrocycle which adopts a “pocket-like” conformation. Potentiometric and ³⁵CI NMR experiments demonstrate that 2-6H⁺ also binds CI^? in aqueous solution. Subsequent extensive molecular dynamics computational studies starting from X-ray coordinates show that the solid state structure is representative of the solution conformations for I-6H⁺, whereas the conformations of 2-6H⁺ are strongly affected by intramolecular interactions between the ammonium centres and O-atoms of the ether linkage as well as by intermolecular interactions with H₂O molecules and CI^? counterions.     

N-对甲基苄基苯甲酰胺的固相合成及其晶体结构分析

标题化合物采用固相法合成: 聚苯乙烯磺酰氯树脂1与对甲基苄胺反应得到N-对甲基苄基磺酰胺树脂2, 用苯甲酰氯酰化得到N-对甲基苄基-N-苯甲酰基磺酰胺树脂3。用TiCl4/Zn/THF处理从树脂3上经自由基解脱的方法得到N-对甲基苄基苯甲酰胺4, 产率为76%。晶体结构在Bruker SMART 1000 CCD X-射线衍射仪上, 用石墨单色器单色化的MoK嵘湎?l = 0.071073 nm)测定。非氢原子坐标用直接法解出, 用最小二乘法对非氢原子进行各向异性温度因子修正。N-对甲基苄基-苯甲酰胺: 化学计量式为: C15H15NO, Mr = 225.28, 晶体属于正交晶系, Pna21空间群。晶胞参数: a = 0.9549(6), b = 1.1169(7), c = 1.1774(7) nm, V = 1.2557(13) nm3, Z = 4, Dc = 1.192 g/cm3, m = 0.075 mm-1, F(000) = 480;最终结构偏离因子R = 0.0478, wR = 0.1013, S = 0.912。化合物4的晶体结构中有分子间氢键相互作用。     

Phase Diagrams of the Ternary Gas Hydrate Forming Systems at High Pressures. Part II. Ethane–Methane–Water System

The sections of the phase diagram of a ternary system ethane–methane–water at pressures up to 1000 MPa were studied by means of the differential thermal analysis. The investigation was carried out under the conditions of excessive amount of the gas. It was established that two continuous rows of solid solutions belonging to the II type according to Rosenbom’s classification (with a maximum) exist within the whole pressure range studied: one of them is based on the cubic structure I (CS-I) and another on the cubic structure II (CS-II). With an increase in pressure, the maxima at the decomposition curves of solutions based on CS-II shift towards the hydrates with higher ethane content. This was explained in terms of intrusion of ethane molecules into the small d-cavities of the CS-II which is caused by the pressure imposed.     

Star/Linear Polymer Topology Transformation Facilitated by Mechanical Linking of Polymer Chains

Topology transformation of a star polymer to a linear polymer is demonstrated for the first time. A three‐armed star polymer possessing a mechanical linking of two polymer chains was synthesized by the living ring‐opening polymerization of δ‐valerolactone initiated by a pseudo[2]rotaxane having three hydroxy groups as the initiator sites on the wheel component and at both axle termini. The polymerization was followed by the propagation end‐capping reaction with a bulky isocyanate not only to prevent the wheel component deslippage but also to introduce the urethane moiety at the axle terminal. The resulting rotaxane‐linked star polymer with a fixed rotaxane linkage based on the ammonium/crown ether interaction was subjected to N‐acetylation of the ammonium moiety, which liberated the components from the interaction to move the wheel component to the urethane terminal as the interaction site, eventually affording the linear polymer. The physical property change caused by the present topology transformation was confirmed by the hydrodynamic volume and viscosity.     

基于电纺纳米纤维的固相萃取技术

纳米纤维极具优越固相萃取介质的潜质,基于纳米纤维的固相萃取法( Nanofibers based solid phase extraction, NFs-SPE)已成为新兴的样品预处理技术。本文在评述NFs-SPE在食品、环境样品、生物样品等实际样品检测应用的相关研究基础上,提出纳米纤维的分子结构和形态结构与目标物吸附效能之间存在着“结构”-“效应”关系,这将是明确纳米纤维高效吸附目标物的机理的关键突破口。     

Analysis of the Phase Changes During Evaporation of Emulsions with Different Oil Phases

Emulsions surfer alterations in their microstructure after applied on the skin, because of the interaction with skin constituents and mainly by the evaporation of volatile components. These alterations are not even considered by cosmetic formulators, but they are extremely important because they can act on formulation stability, on delivery and on permeation of actives and also on the ability to build the occlusive film, responsible for skin's moisturization. This research studied the phase changing during evaporation of emulsions made with three different oil phase: mineral oil, avocado oil, and isocethyl/stearoil stearate, as a function of the decrease on water ratio, using phase diagrams and evaporation test. It was observed the formation of liquid crystalline phases and their transition along the evaporation path for emulsions with the three different oil phases. It was also observed that these transitions occurred in different water ratios.     

应用相图边界理论勾画多元恒温截面相图

根据相图的边界理论,可以确定恒温截面图中紧邻相区及其边界关系,进而可以根据有限的实验数据,比较直接地勾画出整个恒温截面图。本文以5元相图和8元相图为例加以说明。     

掺锌的TiO2纳米粉的结构相变及发光性质

采用溶胶-凝胶法制备了掺锌的TiO₂纳米粉末,并用XRD、TEM、TG和DSC等技术考察了掺入的锌对TiO₂的锐钛矿→金红石结构相变的影响.研究结果表明,锌的掺入可促进TiO₂的结构相变,使相变温度显著降低.纳米态TiO₂存在室温光致发光现象,在TiO₂的纳米粉中掺入适量的锌,可显著增强体系的发光强度.     

二组分固-液系统复杂相图的讨论式教学

将讨论式教学法的基本思想应用到物理化学课程的教学难点——二组分固-液系统复杂相图中，并进行深入讨论，最终归纳总结出此类相图普遍适用的基本规律，以便于学生熟练掌握复杂相图的分析方法，为后续课程的学习及实际应用打下良好的理论基础。     

N-2-氯苄基苯甲酰胺的固相合成及其晶体结构分析

N-2-氯苄基苯甲酰胺采用固相法制备.聚苯乙烯磺酰氯(1)在吡啶存在下与2-氯苄胺反应得到N-2-氯苄基磺酰胺树脂(2),进一步在吡啶催化下用苯甲酰氯进行酰化得到N-2-氯苄基-N-苯甲酰基磺酰胺树脂(3).用TiCl₄/Zn/THF试剂处理,从树脂3上解脱得到产物N-2-氯苄基苯甲酰胺(4),产率92%.N-2-氯苄基苯甲酰胺的晶体属于单斜晶系,P2₁空间群,晶胞参数:a=0.7149(3)_nm,b=0.8772(4)_nm,c=0.9704(4)_nm;β=95.172(7)°;晶体结构中存在两种分子间氢键相互作用.     

固体C60中取向运动模型与结构相变温度的计算

提出了不同温度范围内固体C₆₀分子取向运动模型,从微观上探索了取向相变发生的原因,并根据这些模型计算了面心立方及取向玻璃态的转变温度T_c及T_g,结果与实验颇相符合。