MICROENVIRONMENTAL EFFECTS OF THE HELICAL CONFORMATIONS OF AMYLOSE AND ITS DERIVATIVES——CATALYTIC EFFECTS OF SODIUM CARBOXYMETHYLAMYLOSE ON THE HYDROLYSIS OF VARIOUS ESTERS OF N-ALKYL-3-HYDROXYPYRIDINIUM IODIDE

Hydrolysis of various carboxylic esters of N-alkyl-3-hydroxypyridinium iodide(2—5) has been studied, both in the absence and in the presence of sodium carboxymethylamylose(NaCMA 1). In the absence of Na-CMA, the hydrolysis of all four substrates follows 2nd-order kinetics when HPO_4~- and CH_3CO_2~- ions are used as the attacking nucleophites. In the presence of 1, however, the course of the reaction depends on the structure of the substrates. For 2 and 3, the observed rate constants k_(obs) are independent of the eoncentration of 1 added, but for those with long hydrocarbon chains, i. e. 4 and 5, the hydrolysis follows MichaelisMenten kinetics. All other experimental results also indicate the formation of supramolecular(incluston) complexes between the Na-CMA host molecules in helical conformations and theesters 4 and 5. In comparison with the bimolecular processes in the bulk phase, the catalytic efficiencies(k_c/K_d) of these supramolecular systems are 3.7×10~4 and 1.7×10~4 times that of the aceta     

柔性烃链定位光氯化反应的初步研究

对于刚性分子的远距离定位光卤化反应已有成功的报导,柔性链分子由于不易找到合适的环境或基架来控制链的定向,因此定位反应遇到很大困难。本工作则试图利用处于反向胶团中疏水分子的相对有序排列的特性来对柔性链分子定位的光氯化反应作试探性研究。合成了不同长度的对-碘代苯基羧酸I-C_6H_4-(CH_2)_nCOOH(1)并与反应受物正十二醇生成相应的酯,经与氯气反应生成二氯碘代苯基羧酸十二酯Cl_2I-C_6H_4-(CH_2)_nCOOC_(12)H_(25)(2),将(2)     

基于极大似然估计的BP算法及其在深基坑开挖参数辨识中的应用

本文采用人工神经网络BP算法对深基坑开挖工程中的参数进行辨识,将某些现场实测值作为网络输入,土层物性参数作为网络的输出, 限元计算取得学习样本来训练网络,从而地深基坑开挖工程中的参数进行辨识的目的,同时,本文提出了将极大似然估计引入BP学习算法中,可以考虑学习样本和网络输入（现场产测值）的误差,可以求得所辨识参数的可靠度,本文还对动态调整BP学习算法的学习速度因子,冲量系数以加快网络学习速度的算法进行了研究,本文算例表明本文算法训练速率可比传统BP算法快10倍以上。     

高温闪烁晶体Ce∶YAP的生长研究

Ce∶YAP晶体具有优良的闪烁性能,其主要特点是光产额大,衰减时间短,发射峰与光电倍增管的接收范围相匹配,在γ射线探测、核医学等方面有着广阔的应用前景.我们用提拉法生长了不同掺杂浓度的Ce∶YAP晶体,成功地解决了在生长过程中出现的晶体开裂及孪晶问题,并对晶体生长过程中的爬料、纯YAP晶体着色等现象作了讨论.X射线激发发射谱表明晶体的发射峰在388nm,吸收测试则显示晶体在254nm、366nm处有两个吸收峰.     

YAP晶体变色现象的研究

YAlO3(YAP)晶体具有优良的物理和化学性能,在许多方面都有广泛的应用前景.我们在对闪烁晶体Ce∶YAP的研究过程中,发现了YAP晶体的变色现象.本文利用晶体透过谱对其颜色的变化进行了研究.不同的退火气氛及不同的掺杂成份对晶体颜色有较大影响,H2气氛退火或掺杂Ce元素使晶体颜色变浅,而在空气中退火或掺杂Yb元素则使晶体颜色加深.针对这一变色现象,我们认为是在晶体生长过程由于电荷补偿的需要而产生的O-心的吸收作用导致的.不同的O-心浓度其吸收作用不同,从而使晶体在400nm附近的透过率发生变化.采用这一模型可以对晶体颜色的变化及不同退火条件和掺杂元素的影响作出合理的解释.     

Electron-transfer fluorescence quenching processes in coaggregates between excited N-alkylcarbazoles as electron donors and 2, 4-dinitrophenyl carboxylates or pentafluorophenyl carboxylates as acceptors

Electron-transfer processes facilitated by hydrophobic-lipophilic interaction ( HLI) between excited N-alkylcar-bazoles (1-n, n=4, 8, 12, 16) as electron donors and 2,4-dintrophenyl carboxylates (2-n, n = 4, 8, 12, 16) or pentafluorophenyl carboxylates (3-n, n = 4, 8, 12, 16) as electron acceptors have been investigated by means of fluorescence spectroscopy in aqueous or aquiorgano binary mixtures. The fluorescence quenching of -n * by 2-n or -n indicates that preassociation precedes the electron transfer. The extent of HLI-driven coaggregation of the acceptor and the donor may be assessed from the B value of the equation I0/I = A B [Q]. The chain-length effect and possibly also a chain-fold-ability effect, as well as the solvent aggregating power (SAgP) effect have been observed. Comparison of the quenching constants (B) for 1-n * /2-n combinations and 1-n * / 3-n combinations shows that the order of increasing R values for the quenching processes is 3-n < 2-n.     

Aggregating tendencies of some N-alkylcarbazoles

Aggregation of some nitrogen-containing heterocyclic compounds have been investigated by means of fluorescence spec-troscopy in aqueous or aquiorgano binary mixtures of different Φ values for the first time. The aggregators studied are N-butylcarbazole (CBZ-4), N-octylcarbazole (CBZ-8), N-do-decylcarbazole (CBZ-12), and N-hexadecylcarbazole (CBZ-16). Their aggregating tendencies have been evaluated by measuring their critical aggregate concentration values (CAgC's). Our results indicate that the N-alkylcarbazoles, just like the anthracene derivatives with different chain-lengths, can also be used as fluorescence probes for evaluating aggregating tendencies or CAgC values.     

结构分析有限元程序JIGFEX和它的新发展

本文简要介绍了结构静、动力有限元分析程序ＪＩＧＦＥＸ的主要特色和它在土与结构相互作用、饱和土分析、动态子结构分析、非线性接触分析、高层建筑抗震分析、温度场与热传导分析、群论结构分析以及平稳与非平稳多点随机地震激励响应分析等多方面最新发展．     

混凝土中化学-热-湿-力耦合过程的数值方法

提出了一个火灾下混凝土中化学-热-湿-力耦合过程分析的两级数学模型. 混凝 土模型化为充满两种非混溶孔隙流体的非饱和变形多孔多相介质. 数学模型基于控制干空 气、湿份及基质溶解物的质量守恒、混凝土介质混合体的动量守恒和焓(能量)守恒的耦合 偏微分方程组. 模型中特别考虑到了高温下的脱盐过程. 构造了一个用于数值模拟 化学-热-湿-力耦合行为的有限元求解过程的混合弱形式. 并且针对其中具有非自伴随算子特性的 双曲线控制方程的空间离散进行了特殊考虑. 数值结果例题显示所发展的数学模型和数值方 法在重现火灾条件下的混凝土中化学-热-湿-力耦合行为的有效性.     

广义对流扩散方程的隐式特征线混合元方法

提出了一个广义对流扩散方程的混合有限元方法，方程的基本变量及其空间梯度和流量在单 元内均作为独立变量分别插值. 基于胡海昌-Washizu三变量广义变分原理结合特征线法给 出了控制方程的单元弱形式. 混合元方法采用基于一点积分方案并结合可以滤掉虚假的 数值震荡的隐式特征线法. 数值结果证明了所提出的方法可以提供和四点积分同样的数 值计算结果，并能够提高计算效率.