ELASTIC BEHAVIOR OF PROTEIN-LIKE SINGLE CHAIN

The conformational properties and elastic behaviors of protein-like single chains in the process of tensile elongation were investigated by means of Monte Carlo method. The sequences of protein-like single chains contain two types of residues: hydrophobic (H) and hydrophilic (P). The average conformations and thermodynamics statistical properties of protein-like single chains with various elongation ratio λ were calculated. It was found that the mean-square end-to-end distance r increases with elongation ratio,λ. The tensor eigenvalues ratio of : decreases with elongation ratio λ for short (HP)x protein-like polymers, however, the ratio of : increases with elongation ratioλ,especially for long (H)x sequence. Average energy per bond increases with elongation ratioλ, especially for(H)x protein-like single chains. Helmholtz free energy per bond also increases with elongation ratioλ. Elastic force (f), energy contribution to force (fU) and entropy contribution to force (fs) for different protein-like single chains were also calculated.These investigations may provide some insights into elastic behaviors of proteins.     

MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.     

脲、盐酸胍对碳氢链疏水作用的影响

本文测定了不同脲、盐酸胍浓度下,Triton X-100溶液的临界胶团浓度(cmc)和肌酸激酶分子在溶液中的暴露巯基数.通过计算脲、盐酸胍引起的Trito X-100胶团化过程中碳氢链的疏水能改变值,得到了评价脲、盐酸胍对碳氢链疏水作用影响的参数,盐酸胍降低碳氢链疏水能的能力是脲的3.5倍.实验结果还表明,盐酸胍引起肌酸激酶内坦巯基暴露的能力约为脲的3.2倍,这意味首在一定浓主工范围内脲、盐酸胍引起肌酸激酶变性的主要因素是它们降低了碳氢链的疏水作用.     

稀土胺羧酸配合物的研究 I. {[MnGd(DTPA)(H2O)5]2·H2O}n配合物的合成和晶体结构

本文首次合成了{MnLn(DTPA)(H2O)5]·H2O}n异核链式配合物(Ln=Gd, Er, Y)单晶,测定了{[MnGd(DTPA)(H2O)5]2·H2O]n的单晶结构。     

微乳液的热力学性质 I: 芳烃类的侧链链长对微乳液热力学函数影响

本文研究以非离子型表面活性剂-正辛醇-水-芳烃类所组成的微乳液, 探讨醇从油相转移到界面相时的自由能变化, 以及温度对自由能的影响。计算出熵和焓的变化, 发现在实验范围内, 上述热力学函数的对数值与芳烃侧链的碳原子数(n)呈线性关系。这些关系式对微乳液的构成和稳定性的讨论是重要的, 还对几种芳烃异构体所构成的微乳液的热力学函数进行了实验和讨论。     

2,5-噻吩齐聚物链结构的表征

本文合成、分离和纯化了一系列2,5-噻吩齐聚物(n=2-5),作为聚噻吩的模型化合物.首次系统报道了这类化合物的质谱、^1H、^1^3C核磁共振谱和红外光谱,以对其结构进行表征,所得结果与用电化学方法制备的中性聚噻吩的相应结果进行比较,表面聚噻也具有α-α'连结的结构.     

聚合物链构象的研究I: 1,2-聚丁二烯的构象分析

本文应用Flory的链分子统计理论研究1,2-聚丁二烯的链构象,选择固定键长和键角的分子模型,计算构象能,构成势能面图,并由势能面的构型积分,得到了表征1,2-聚丁二烯链构象特征的统计权重矩阵.     

疏水-亲脂相互作用对反应性的影响2.长链分子簇集和绕曲的溶剂效应

研究了一系列不同链长的对硝基苯酚羧酸酯在十种有机溶剂和水的二元混合溶剂中的水解反应,有机溶剂的体积含量分别为30％(Φ=0.30)和50％(Φ=0.50).结果表明,在Φ=0.50的各溶剂体系中,只有乙二醇-水和二甲亚砜-水体系,十六酸酯的水解速度才因受物分子的簇集绕曲而减慢.而在Φ=0.30的各溶剂体系中,除t-BuOH-H_2O体系外,十六酸酯全都存在簇集和绕曲现象,水解速度因此而受抑制的程度有如下次序:乙二醇>二甲亚砜>乙二醇单甲醚>二甲基甲酰胺～乙二醇二甲醚>二氧六环>乙醇～丙酮～乙腈>叔丁醇.如以log(k_(C8)/k_(a16))值作为衡量溶剂对受物的疏水-亲脂作用大小的定量标准,则发现各log(k_(C8)/k_(a16))和有机溶剂的介电常数ε,溶剂极性标度Kosower’s Z值,Dimroth’sE_T(30)值及Taft’s π值都不相关,但和Rekker的疏水常数f值却有较好的相关关系.这说明在这些“促簇性”溶剂中,控制长链酯水解的主要因素是疏水-亲脂相互作用,而和溶剂的极性无直接关系.此外,还讨论了不同比例的二元溶剂体系中水解的活化参数△S,△H.本工作首次提供了Rekker疏水常数应用于研究有机化合物反应性的实例.