含特殊官能团有机物分配系数预测的多参数线性自由能关系(PP-LFERs)研究
Polyparameter linear free energy relationships (PP-LFERs) for predicting partition coefficients of organic compounds with specific functional groups
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摘要: 利用多参数线性自由能关系（PP-LFERs）模型预测有机物的有机碳-水分配系数（Koc）是一种高效经济的估算方法.基于广泛收集的文献中165种（18类）化合物的lgKoc和分子结构参数（E、S、A、B、V）值，通过多元线性回归方法，用建模组132种化合物构建了两种预测多种类有机物lgKoc的PP-LFERs模型：EV模型和简化的V模型.它们的复相关系数分别为0.92和0.87，标准误差分别为0.37和0.49.用验证组33种化合物对模型进行了验证的结果表明，两种模型均具有较好的预测性和稳健性.在数据集中包括有8种典型的高氟和硅氧烷类化合物，对于硅氧烷类化合物，EV模型和V模型的实测值和预测值的均方根误差分别为0.38和0.16；对于高氟类化合物，两模型的均方根误差分别为0.66和0.75，说明了模型对这两类化合物预测的准确性.最后，从分子间作用力角度分析了有机物的吸附机理，得出空穴作用和色散作用是非极性化合物吸附的主要动力，而在极性化合物中，空穴作用和氢键作用最为显著.
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关键词:
- 线性自由能关系(LFERs) /
- 分子结构参数 /
- 有机碳-水分配系数 /
- 高氟和硅氧烷类化合物 /
- 吸附 /
- 分子作用力
Abstract: Polyparameter linear free energy relationships (PP-LFERs) have been proven to be an efficient and economic evaluation method to predict organic carbon-water partition coefficient (Koc) of organic compounds. Based on the values of lgKoc and molecular descriptors of 165 compounds (18 classes) widely collected in the literatures,two PP-LFERs models,namely EV model and V model for predicting lgKoc,were calibrated with data for a set of 132 compounds,using multiple linear regression method. The values of multiple correlation coefficients were 0.92 and 0.87,respectively. The standard errors between experimental lgKoc and those predicted in the EV model and V model were 0.37 and 0.49,respectively. A set of 33 compounds were utilized for validation. The results showed that the two models had good predictability and robustness. Note that eight typical highly fluorinated and siloxane compounds were included in the data set,and their predictions were sufficiently accurate. For siloxane compounds,root-mean-squared-error between experimental lgKoc and predicted ones was 0.38 in the EV model and 0.16 in the V model;and for highly fluorinated compounds,root-mean-squared-error was 0.66 in the EV model and 0.75 in the V model. Finally,the sorption mechanism was discussed based on the molecular interactions. The effect of cavity and dispersion played an important role in the sorption of nonpolar compounds,while cavity formation and H-bonding interaction were dominant in the sorption of polar compounds. -
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