Feng Changjun and Du Xihua.Theoretical models for predicting the bioconcentration factors of halogenated benzenes in fish[J].Journal of Shenzhen University Science and Engineering,2014,31(1):96-102.[doi:10.3724/SP.J.1249.2014.01096]





Theoretical models for predicting the bioconcentration factors of halogenated benzenes in fish
徐州工程学院化学化工学院,江苏 徐州 221111
Feng Changjun and Du Xihua
School of Chemistry and Chemical Engineering, Xuzhou Institute of Technology, Xuzhou 221111, Jiangsu Province, P.R.China
computational chemistry halogenated benzene bioconcentration factor density functional theory(DFT) thermodynamic analysis quantitative structure-activity relationship(QSAR)
TQ 242.1; O 6-051
基于密度泛函理论 (density functional theory, DFT)对21种卤代苯化合物进行结构优化,并用最佳变量子集回归分析方法研究它们在鱼体内的生物富集因子(bioconcentration factors, BCF). 在DFT方法的较高基组B3LYP/6-311G**(d,p)水平下,计算上述分子的平衡几何构型、前线轨道能、原子Mulliken电荷和热力学性质. 研究发现,上述分子的lgBCF和次最低空轨道能(ENLUMO)、配分函数(lgQ)、苯环的第2个碳原子上净电荷(Q2)具有良好的线性关系. 经逐一和逐五剔除交互验证,以及AC、KT和tα/2检验,所建构效关系(quantitative structure-activity relationship, QSAR)模型具有良好的稳健性和预测能力. 根据所建QSAR模型建议卤代苯分子在鱼体内可能的生物富集机理. 经热力学分析,卤代苯类化合物在鱼体内的生物富集过程中的焓变起到主要及正向作用,熵变(主要是疏水性作用)则起次要及负向作用.
The quantitative structure-activity relationship (QSAR) between structures and bioconcentration factors (BCF) of 21 halogenated benzenes in fish was studied by using both density functional theory (DFT) and leaps-and-bounds regression analysis methods. The equilibrium geometries, the frontier molecular orbital energy, thermodynamic properties and Mulliken charges of atoms in these compounds have been calculated by the DFT method on the basis of the B3LYP/6-311G**(d,p) set. It is found that there are good linear relationships between the experimental lgBCF for the molecules and the calculated parameters such as energy of the next lowest unoccupied molecular orbital (ENLUMO), partition function (lgQ), net charge (Q2) of the second carbon atom in the benzene ring respectively. Based on the results of Rcv-o2, Rcv-f2 of leave-one and five-out cross-validation, Akaike’s information criterion (AC) and Kubinyi function (KT), tα/2, it is discovered that this established QSAR model has good stability and predictability. The possible mechanism for the bioconcentration of halogenated benzenes in fish is thus proposed according to the QSAR model. On the basis of the thermodynamic analysis, enthalpy change plays a primary and positive role during bioaccumulation of halogenated benzene compounds in fish, however, entropy change (mainly hydrophobic interaction) plays a secondary and negative one.


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Foundation:National Natural Science Foundation of China (21075138); Special Fund of State Key Joint Laboratory of Environment Simulation and Pollution Control (13K02ESPCT)
Corresponding author:Professor Feng Changjun. E-mail: fengcj@xzit.edu.cn
Citation:Feng Changjun, Du Xihua. Theoretical models for predicting the bioconcentration factors of halogenated benzenes in fish[J]. Journal of Shenzhen University Science and Engineering, 2014, 31(1): 96-102.(in Chinese)
作者简介:冯长君(1954-),男(汉族),江苏省新沂市人,徐州工程学院教授. E-mail: fengcj@xzit.edu.cn
引文:冯长君,堵锡华.卤代苯在鱼体内生物富集因子的理论模型[J]. 深圳大学学报理工版,2014,31(1):96-102.
更新日期/Last Update: 2014-01-08