Chloronaphthalenes (PCNs, polychlorinated naphthalenes) are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed...Chloronaphthalenes (PCNs, polychlorinated naphthalenes) are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed for all 75 PCNs at the HF/6-31G^* level of theory. A number of statistic based parameters have been extracted. Linear relationships between gas-chromatographic retention index (RI) of 62 PCNs in a non-polar column (DB-5) and the structural descriptors have been established by stepwise multiple regression technique. The result shows that two quantities derived from electrostatic potential on molecular surface, ∑Vs- and σ+^2, together with the number of chlorine ( NCl ) and the energy of the highest occupied molecular orbital (EHOMO) can be well used to express the quantitative structure-retention relationship (QSRR) of PCNs. Predictive capability of the model has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient (Rcv^2) of 0.997, and further compared with the results from similar researches published recently. Furthermore, when splitting the 62 PCNs into training and validation sets in the ratio of 2:1, a similar treatment yields an equation of almost equal statistical quality and very similar regression coefficients, validating the robustness and prediction capability of our model. The QSRR model established may provide a new powerful method for predicting chromatographic properties of polychlorinated naphthalenes.展开更多
基金Supported by the Analysis and Measurement Planning Project of Zhejiang Province (2007F70053)
文摘Chloronaphthalenes (PCNs, polychlorinated naphthalenes) are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed for all 75 PCNs at the HF/6-31G^* level of theory. A number of statistic based parameters have been extracted. Linear relationships between gas-chromatographic retention index (RI) of 62 PCNs in a non-polar column (DB-5) and the structural descriptors have been established by stepwise multiple regression technique. The result shows that two quantities derived from electrostatic potential on molecular surface, ∑Vs- and σ+^2, together with the number of chlorine ( NCl ) and the energy of the highest occupied molecular orbital (EHOMO) can be well used to express the quantitative structure-retention relationship (QSRR) of PCNs. Predictive capability of the model has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient (Rcv^2) of 0.997, and further compared with the results from similar researches published recently. Furthermore, when splitting the 62 PCNs into training and validation sets in the ratio of 2:1, a similar treatment yields an equation of almost equal statistical quality and very similar regression coefficients, validating the robustness and prediction capability of our model. The QSRR model established may provide a new powerful method for predicting chromatographic properties of polychlorinated naphthalenes.