单取代烷烃定量结构-保留相关研究中的分子结构分区处理方法

将单取代烷烃RX(X=卤素,OH,SH,NH2等)分子结构分为两个区域(R和X)来提取分子结构参数,从三方面影响因素(烷基R、取代基X、R与X的相互作用)来定量关联RX的气相色谱保留时间。实验测定了37种单取代烷烃RX的气相色谱保留时间,并以键连接矩阵特征根之和EVM、烷基极化效应指数PEI、取代基质量分数w和取代基上氢原子所带部分正电荷ΔNH 4个参数为变量,建立了定量结构-保留相关模型。该模型具有良好的预测能力和外推能力,对醇在不同色谱柱上的保留指数进行了预测,结果与测定值符合得较好。

Quantitative Structure-Retention Relationships of Monosubstituted Alkanes by Dividing Its Molecular Structure into Substructure

In order to investigate the quantitative structure-retention relationship in gas chromatography (GC) , the molecular structure of monosubstituted alkane RX (X = halogen, OH, SH, NH2) is divided into two parts, R and X, to obtain molecular structure parameters, and the retention times in GC for 37 monosubstituted alkanes RX were determined. It was proposed that the retention time in GC is affected by three main factors for RX compounds, alkyl group R, substituted group X, and interaction between R and X. Using four parameters, the eigenvalue of bonding orbital-connection matrix EVM, the polarizability effect index of alkyl group PEI, the mass content for substituted group X, and the partial charge deltaN(H) on hydrogen atom of the group X, a quantitative structure-retention correlation model with correlation coefficient (r) of 0.9948 and standard deviation (S) of 0.0991 was obtained for the 37 RX compounds. The model obtained has good predictive and extrapolation ability. The predicted retention indexes are in good agreement with the experimental ones for alcohols.