首页|基于SMD模型预测全/多氟烷基化合物的正辛醇-水分配系数

基于SMD模型预测全/多氟烷基化合物的正辛醇-水分配系数

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全/多氟烷基化合物(PFASs)是备受关注的新污染物。正辛醇-水分配系数(KOW)是评价化学品在环境中分配、迁移和归趋的重要参数，但大多数PFASs缺少KOW的实测值。发展可靠的KOW预测方法，对填补PFASs的KOW数据缺失具有重要意义。本研究通过基于溶质电子密度的溶剂化模型(SMD)描述溶剂化效应，以19种PFASs的lgKOW实测值为参照，从哈特里-福克自洽场和密度泛函理论与不同基组的组合中，筛选适于预测PFASs的lgKOW方法。比较lgKOW实测值与不同方法所得预测值之间的相关系数®和均方根误差(RMSE)，发现当用B3LYP泛函结合6-31+G(d，p)基组优化几何结构，B3LYP泛函结合MIDI!6D基组计算能量时，预测效果最好(r=0。980，P＜0。001，RMSE=0。273)。发现溶剂形成空穴、溶质-溶剂色散作用和溶剂局部结构变化，为PFASs的KOW值的主要影响因素。本研究为预测PFASs的KOW提供了一种可行的方法。
Prediction of octanol-water partition coefficients of per-and polyfluoroalkyl substances based on SMD model
Per-and polyfluoroalkyl substances(PFASs)are emerging pollutants with increasing concern.Octanol-water partition coefficient(KOW)is an important parameter for assessing the distribution,transport and fate of chemicals in the environment.However,most PFASs lack KOW values.It is of significance to develop a reliable method for predicting the KOW values of PFASs and filling the data gap.In this study,using the solvation model based on solute electron density(SMD)to mimic solvation effects and the experimental lgKOW data of 19 PFASs as references,a suitable method for predicting lgKOW values of PFASs was determined by evaluating the combination of Hartree-Fock self-consistent field and density functional theory with different basis-sets.Correlation coefficient(r)and root mean square error(RMSE)were adopted to compare the experimental and calculated lgKOW values from different methods.The optimum prediction results(r=0.980,P＜0.001,RMSE=0.273)were achieved using geometric structures optimized by the B3LYP functional with the 6-31+G(d,p)basis-set,and energy calculated using the B3LYP functional with the MIDI!6D basis-set.It was found that solvent cavitation,dispersion between the solute and solvent,and changes in local solvent structures are the main factors affecting the KOW values of PFASs.This study offers a feasible method for predicting the KOW values of PFASs.

per-and polyfluoroalkyl substancesoctanol-water partition coefficientsHartree-Fock self-consistent fielddensity functional theorysolvation model based on solute electron density

江波、陈景文、肖子君、苏利浩

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工业生态与环境工程教育部重点实验室,大连市化学品风险防控及污染防治技术重点实验室,大连理工大学环境学院,大连,116024

全/多氟烷基化合物 正辛醇-水分配系数 哈特里-福克自洽场 密度泛函理论 基于溶质电子密度的溶剂化模型

国家自然科学基金国家重点研发计划

221360012022YFC3902100

2024

10.7524/j.issn.0254-6108.2023041404

环境化学
中国科学院生态环境研究中心

环境化学

CSTPCD北大核心
影响因子：1.049
ISSN：0254-6108
年,卷(期)：2024.43(4)
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