DFT and Position of Cl Substitution (PCS) Methods Studies on n-Octanol/water Partition Coefficients (lgK_(ow)) and Aqueous Solubility (–lgS_w) of All PCDD Congeners  

作　　者：谢亚杰 赵惠明 王遵尧 张雅荣 

机构地区：[1]School of Biological and Chemical Engineering, Jiaxing University

出　　处：《Chinese Journal of Structural Chemistry》2007年第12期1409-1418,共10页结构化学（英文）

基　　金：This work was supported by the National Natural Science Foundation of China (No. 20737001)(2003CB415002);China Postdoctoral Science Foundation (No. 2003033486)

摘　　要：Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.

关 键 词：polychlorinated dibenzo-p-dioxins （PCDDs） n-octanol/water partition coefficients（lgKow） aqueous solubility （-lgSw） quantitative structure-property relationship （QSPR） DFT position of CI substitution （PCS） method 

分 类 号：O621.2[理学—有机化学]