基于SMD模型预测全/多氟烷基化合物的正辛醇-水分配系数  

Prediction of octanol-water partition coefficients of per-and polyfluoroalkyl substances based on SMD model

作　　者：江波 陈景文[1] 肖子君 苏利浩 JIANG Bo;CHEN Jingwen;XIAO Zijun;SU Lihao(Key Laboratory of Industrial Ecology and Environmental Engineering(Ministry of Education),Dalian Key Laboratory on Chemicals Risk Control and Pollution Prevention Technology,School of Environmental Science and Technology,Dalian University of Technology,Dalian,116024,China)

机构地区：[1]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

出　　处：《环境化学》2024年第4期1107-1117,共11页Environmental Chemistry

基　　金：国家自然科学基金(22136001);国家重点研发计划项目(2022YFC3902100)资助.

摘　　要：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(K_(OW))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K_(OW)的实测值.发展可靠的K_(OW)预测方法,对填补PFASs的K_(OW)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lgK_(OW)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lgK_(OW)方法.比较lgK_(OW)实测值与不同方法所得预测值之间的相关系数(r)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K_(OW)值的主要影响因素.本研究为预测PFASs的K_(OW)提供了一种可行的方法.Per-and polyfluoroalkyl substances(PFASs)are emerging pollutants with increasing concern.Octanol-water partition coefficient(K_(OW))is an important parameter for assessing the distribution,transport and fate of chemicals in the environment.However,most PFASs lack K_(OW) values.It is of significance to develop a reliable method for predicting the K_(OW) 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 lgK_(OW) data of 19 PFASs as references,a suitable method for predicting lgK_(OW) 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 lgK_(OW) 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 K_(OW) values of PFASs.This study offers a feasible method for predicting the K_(OW) values of PFASs.

关 键 词：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 

分 类 号：X50[环境科学与工程—环境工程]