有机化合物的构性相关分析Ⅲ.卤代烃的构性相关分析

简明地描述了极性共价键概念 ,并用成键原子的电负性差说明了卤代烃分子中的 C— X(X为 F,Cl,Br,I)键都是极性共价键。同时 ,在有机化学构性相关理论指导下 ,对卤代烃进行了较系统的构性相关分析 ,揭示了它们构性之间的因果关系规律 ,并将其化学性质归纳成 3大类 :官能团的反应 ,烃基的反应 ,官能团和烃基共同参与的反应。     

Electronegativity Scale of Elements Calculated by Density Functional Theory and Related Methods

In chemistry and many related fields, electronegativity (EN) is an important fundamental concept and its scale is a useful physcochemical parameter. Here, calculations of both ionization potentials and electron affinities are extended toward 107 elements and done by density functional theory at the local density approximation(LDA) level and the LDB level, i.e., the local density approximation level with further non-local corrections for exchange and correlation included self-consistently as well as the modified Slater transition-state method. The definite-differentiation method is employed into calculations of the electronegativity scale and the related parameters of 107 elements with very good results due to the consideration of relativistic effects. The calculation presented is to examine both the LDA and LDB approximations in calculations for the ionization potential and electron affinity of the elements with an improved or modified Slater transition-state method, and relativistic effects have also been taken into account for 107 elements compared with 103, 86 or less in the previous report under a spin polarized density function theory with some approximations to the exchange-correlation function. The calculation results for the various quantities represent an obviously improvement over some previous calculations. It is shown that the results calculated by the extended technique and the improved Slater transition-state method in general agree well with experimental values presented by Pearson, and are better than the reported values in many previous literatures. The developed new electronegativity scale will widely be applicable in many fields such as molecular structural parameterization expression, chemobiological activity optimization prediction, structure-activity quantitation modeling, functional chemical adaptization designing, and so on.     

Density Functional Theory Compute on Electronegativities to Superconductivity of Oxides

In this article we have worked out the correlation between electronegativity and high temperature superconductivity for oxide. It is suggested the equalized electronegativity, X cq , can be used as a empirical criterion for superconductivities of oxides. For determining the X cq , a new formula for the calculation of X cq values has been obtained The X cq values of 230 oxide superconductors have been calculated. The result shows that the X cq values of all the oxide superconductors concentrate in a narrow range from 5.00 to 5.63 and that the oxides with values out side this region would be non-superconductive. This criterion can be applied to almost all the oxide superconductors. It is clearly that this result is able to benefit further inquiries about the mechanism of superconductivity.     

有机物对孔雀鱼急性毒性的电性距离矢量模型研究

[目的]建立一种预测有机物对孔雀鱼急性毒性(pLC50)的定量结构-活性相关性(QSAR)模型。[方法]基于化学拓扑理论,计算了19种有机物的分子电性距离矢量(Md)。运用多元统计回归方法,建立这些有机物对孔雀鱼pLC50与Md的QSAR模型。[结果]经最佳变量子集回归,建立了它们的最佳三元数学模型,传统的判定系数(R2)为0.958,逐一剔除法的交互验证系数(Q2)为0.920。[结论]该模型具有良好的稳健性及预测能力。     

基于电性距离矢量预测新烟碱类杀虫剂的生物活性研究

基于电性距离矢量理论,计算20种重氮乙烷新烟碱类杀虫剂分子的拓扑指数（mk）,经最佳变量子集回归方法建立四元和三元数学模型,并采用逐一法交互检验（R2-cv）、F、A。F-IC、tα/2对所建模型进行检验。结果表明,所建2个QSAR模型具有良好的泛化能力及预测能力,p％_D和pK_A模型的判定系数（R-2）分别为0.955和0．988,R2-cv依次为0．929和0．980;根据pK-D的QSAR模型建议重氮乙烷新烟碱类分子可能的杀虫机理;在影响重氮乙烷新烟碱类化合物作用于果蝇nAChRs的亲和力中-N-、-0基团起到主要及正向作用,而在影响哺乳动物α4β2亚型受体的亲和力中-C-、〉C一更重要且为负向作用。     

三唑噻吩并嘧啶衍生物杀菌活性的QSAR研究

为了研究三唑噻吩并嘧啶衍生物对小麦赤霉菌抑菌活性(G/%)的定量构效关系(QSAR),按照分子的拓扑环境编程计算了14种上述化合物的电性距离矢量(M_D)。通过最佳变量子集回归,建立了它们的二参数(M_(26)、M_(32))QSAR模型,非交叉验证相关系数(R~2)与逐一剔除法交叉验证相关系数(R_(cv)~2)分别为0.857、0.648,显示良好的稳健性和预测能力。根据进入模型可知,影响三唑噻吩并嘧啶衍生物对小麦赤霉菌抑菌活性的主要因素是C-、-O等结构碎片。