Chlorination pattern effect on thermodynamic parameters and environmental degradability for C_(10)-SCCPs: Quantum chemical calculation based on virtual combinational library

作     者：Yuzhen Sun Wenxiao Pan Yuan Lin Jianjie Fu Aiqian Zhang 

作者机构：State Key Laboratory of Environmental Chemistry and Ecotoxicology Research Center for Eco-Environmental Sciences Chinese Academy of Sciences 

出 版 物：《Journal of Environmental Sciences》 (环境科学学报（英文版）)

年 卷 期：2016年第28卷第1期

页      面：184-197页

核心收录：

学科分类：083001[工学-环境科学] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 08[工学] 

基　　金：jointly supported by the Chinese Academy of Sciences (Nos. KZCX2-YW-BR-25, XDB14030500 and YSW2013B01) the National High Technology Research and Development Program (863) of China (No. 2013AA065201) 

主　　题：Short chain chlorinated paraffins(SCCPs) Virtual combinational library Chlorination degree Chlorination dispersion Thermodynamic properties Environmental degradability 

摘      要：Short-chain chlorinated paraffins（SCCPs） are still controversial candidates for inclusion in the Stockholm *** inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors.A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was *** explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical *** thermodynamic properties were acquired using the AM1 method,and frontier molecular orbital analysis was carried out to obtain the EHOMO,ELUMO and ELUMO-EHOMO for degradability exploration at the same *** influence of the chlorination degree（NCl on the relative stability and environmental degradation was elucidated.A novel structural descriptor,μ,was proposed to measure the dispersion of the chlorine atoms within a *** were significant correlations between thermodynamic values and NCl,while the reported NCl-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP *** addition,isomers with largeμ showed higher relative stability than those with small μ.This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and · OH attack *** C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack,while direct photolysis of C10-SCCP congeners cannot readily occur due to the large ELUMO-EHOMO *** chlorination effect and the conclusions were further checked with appropriate density functional theory（DFT） calculations.