Polychlorinated diphenyl ethers(PCDEs) have received more and more concerns as a category of potential persistent organic pollutants(POPs). Modeling its environmental fate and exposure assessment require a number of f...Polychlorinated diphenyl ethers(PCDEs) have received more and more concerns as a category of potential persistent organic pollutants(POPs). Modeling its environmental fate and exposure assessment require a number of fundamental physico-chemical properties. However, the experimental data are currently limited due to the difficulty in analysis caused by the complexity of PCDE congeners. As an alternative, the quantitative structure property relationship(QSPR) approach could be used. In this paper, twelve kinds of molecular connectivity indices(MCIs) of all 209 possible molecular structure patterns of PCDEs were calculated. Based on 106 PCDEs with three observed physico-chemical properties—vapour pressure(P 0 L), aqueous solubility(S w) and n-octanol/water(K ow ) and their MCIs data, a series of QSPR equations were established using multiple linear regression(MLR) method. As a result, three equations with best performance were selected mainly from the view of high regression coefficient(R) and low standard error(SE). All of them showed significant relationship and high accuracy. With these equations the properties of other 103 patterns of PCDEs without the reported observed values were predicted. Furthermore, three partition properties for PCDE congeners—Henry's Law constants(H), partition coefficients between gas/water(K gw ) and gas/n-octanol(K go ) were calculated according to the internal relationship among these six properties. These observed and predicted values, in contrast with the criteria listed in the Stockholm treaty about POPs which has been signed by more than ninety countries in May 2001, illustrated that most of PCDEs congeners are potential persistent organic pollutants. As all descriptors/predictors are derived just from the molecular structure itself and without the import of any empirical parameters, this method is impersonal and promising for the estimation of physico-chemical properties of PCDEs.展开更多
Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy r...Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility （-lgSw） of PCDEs. The model obtained in this work contains two variables： mean molecular polarizability （a） and the most positive partial charge on a hydrogen atom （qH^＋）, of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.展开更多
文摘Polychlorinated diphenyl ethers(PCDEs) have received more and more concerns as a category of potential persistent organic pollutants(POPs). Modeling its environmental fate and exposure assessment require a number of fundamental physico-chemical properties. However, the experimental data are currently limited due to the difficulty in analysis caused by the complexity of PCDE congeners. As an alternative, the quantitative structure property relationship(QSPR) approach could be used. In this paper, twelve kinds of molecular connectivity indices(MCIs) of all 209 possible molecular structure patterns of PCDEs were calculated. Based on 106 PCDEs with three observed physico-chemical properties—vapour pressure(P 0 L), aqueous solubility(S w) and n-octanol/water(K ow ) and their MCIs data, a series of QSPR equations were established using multiple linear regression(MLR) method. As a result, three equations with best performance were selected mainly from the view of high regression coefficient(R) and low standard error(SE). All of them showed significant relationship and high accuracy. With these equations the properties of other 103 patterns of PCDEs without the reported observed values were predicted. Furthermore, three partition properties for PCDE congeners—Henry's Law constants(H), partition coefficients between gas/water(K gw ) and gas/n-octanol(K go ) were calculated according to the internal relationship among these six properties. These observed and predicted values, in contrast with the criteria listed in the Stockholm treaty about POPs which has been signed by more than ninety countries in May 2001, illustrated that most of PCDEs congeners are potential persistent organic pollutants. As all descriptors/predictors are derived just from the molecular structure itself and without the import of any empirical parameters, this method is impersonal and promising for the estimation of physico-chemical properties of PCDEs.
基金funded by the 973 National Basic Research Program of China (2003CB415002)China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility （-lgSw） of PCDEs. The model obtained in this work contains two variables： mean molecular polarizability （a） and the most positive partial charge on a hydrogen atom （qH^＋）, of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.
