摘要
有机磷酸酯(OPEs)是一类备受关注的新污染物,碱催化水解是OPEs降解的重要途径,碱催化水解二级速率常数(kB)是评价其环境持久性的重要参数,但大多数OPEs缺少kB数据.本研究通过比较9种OPEs实验测定与密度泛函理论(DFT)计算的lgkB值,筛选了10种单点能计算方法.发现在IEFPCM/B3LYP/6-311++G(2d,2p)水平进行几何优化,在IEFPCM/B3LYP/6-311++g(3df,2pd)水平计算单点能时,得到的lgkB值与实验测定值拟合效果最好,相关系数(R^(2))为0.93,均方根误差(ERMS)为0.35.结合计算及实验得到的36个kB值,采用极端梯度提升(XGBoost)算法,筛选量子化学等描述符,构建了OPEs的lgkB预测模型,验证集的R^(2)为0.88,ERMS为0.47,三折交叉验证系数(R^(2) CV)为0.70.发现OPEs的kB值在1.26×10^(-8)—8.80×10^(-2) mol^(-1)·L·s^(-1)范围内,含烷基的OPEs不容易水解,其次是含氯代烷基的OPEs,含芳基的OPEs最易水解.所构建的模型为快速、准确预测OPEs的kB值提供方法基础,为评估OPEs的环境持久性提供数据支持.
Organophosphate esters(OPEs)are a class of emerging pollutants.Alkaline hydrolysis is a significant pathway for OPEs degradation,and the second-order rate constant(kB)of alkaline hydrolysis is a crucial parameter for assessing their environmental persistence.However,kB values are largely unavailable for most OPEs.This study compared experimentally measured lgkB values for nine OPEs with those calculated using density functional theory(DFT),and evaluated ten singlepoint energy calculation methods.The best fit between calculated and experimental lgkB values,with a correlation coefficient(R^(2))of 0.93 and a root mean square error(ERMS)of 0.35,was achieved by geometric optimization at the IEFPCM/B3LYP/6-311++G(2d,2p)level and single-point energy calculation at the IEFPCM/B3LYP/6-311++g(3df,2pd)level.By integrating 36 experimental and theoretical kB values,an XGBoost model was developed to forecast lgkB values,utilizing quantum chemical descriptors and others.The R^(2) for the validation set was 0.88,with an ERMS of 0.47,and a three-fold cross-validation coefficient(R^(2) CV)of 0.70.It was observed that the kB values of OPEs ranged from 1.26×10^(-8) to 8.80×10^(-2) mol^(-1)·L·s^(-1),with alkyl-substituted OPEs being less prone to hydrolysis,followed by chloroalkyl-substituted OPEs,while aryl-substituted OPEs were most susceptible to hydrolysis.The constructed model provides a basis for rapid and accurate prediction of kB values of OPEs,thereby supporting the assessment of their environmental persistence.
作者
丁保君
张雅雯
姜琦
陈景文
DING Baojun;ZHANG Yawen;JIANG Qi;CHEN Jingwen(School of Chemical,Dalian University of Technology,Dalian,116024,China;Key Laboratory of Industrial Ecology and Environmental Engineering(Ministry of Education),Department of Environmental Science and Technology,Dalian University of Technology,Dalian,116024,China)
出处
《环境化学》
北大核心
2025年第8期2895-2902,共8页
Environmental Chemistry
基金
国家重点研究发展计划(2022YFC3902100)
国家自然科学基金(22136001)资助.
关键词
有机磷酸酯
密度泛函理论
定量构效关系
碱催化二级水解速率常数.
organophosphate
density functional theory
quantitative structure-activity relationship
base-catalyzed second-order hydrolysis rate constant
作者简介
通信联系人:陈景文,E-mail:jwchen@dlut.edu.cn。
