Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationshi...Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationship（QSAR） models of the bioconcentration factors（BCF） of the anilines in fish were established using some of the following calculated descriptors： EHOMO, ENHOMO, ELUMO, ENLUMO, ΔE1（= ELUMO- EHOMO）, ΔE2（= ENLUMO- ENHOMO）, dipole moment（μ）, molecular volume（V）, vibrational energy of 0 K（Ev）, thermodynamic energy（E）, heat capacity（Cv）, entropy（Sm） and the charge of benzene ring（Qph）. Using the variable selection and leaps-and-bounds regression, the quantum chemical descriptors derived directly from the molecular structures were employed to develop a linear QSAR model between the bioconcentration factors（BCF） and two descriptors（Sm, ENHOMO） of 12 chloroanilines. Statistically, the most significant one is a two-parameter linear equation with the correlation coefficient（R^2） of 0.981 and cross-validated correlation coefficient（Rcv^2） of 0.967. The established QSAR model has good stability and predictability based on the results from Rcv2 of leave-one-out cross-validation, AIC, FIT and tα/2. The quantum chemical analyses were performed from two aspects of frontier molecular orbital and entropy. The results show that two structural describers are crucial to the bioconcentration activity of chloroanilines.展开更多
Contact glow discharge electrolysis of some chloroanilines in sodium sulfate was investigated in different initial concentrations. Each of them underwent the dechlorination, deam-ination through oxidative degradation,...Contact glow discharge electrolysis of some chloroanilines in sodium sulfate was investigated in different initial concentrations. Each of them underwent the dechlorination, deam-ination through oxidative degradation, and were eventually decomposed into hydrogen carbonate and carbon dioxide. It was testified that the chlorine atom and amidogen could be transformed into chloride ion and nitrite ion, respectively. Fe2+ has a remarkable catalytic effect on the degradation of them. On the basis of the detailed analysis of the intermediate products and kinetic behaviors, the reaction pathway was proposed, in which the attack of hydroxyl radical on the benzene ring of starting material might be a key step.展开更多
基金co-financed by the National Natural Science Foundation of China(21075138)special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control(13K02ESPCT)
文摘Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationship（QSAR） models of the bioconcentration factors（BCF） of the anilines in fish were established using some of the following calculated descriptors： EHOMO, ENHOMO, ELUMO, ENLUMO, ΔE1（= ELUMO- EHOMO）, ΔE2（= ENLUMO- ENHOMO）, dipole moment（μ）, molecular volume（V）, vibrational energy of 0 K（Ev）, thermodynamic energy（E）, heat capacity（Cv）, entropy（Sm） and the charge of benzene ring（Qph）. Using the variable selection and leaps-and-bounds regression, the quantum chemical descriptors derived directly from the molecular structures were employed to develop a linear QSAR model between the bioconcentration factors（BCF） and two descriptors（Sm, ENHOMO） of 12 chloroanilines. Statistically, the most significant one is a two-parameter linear equation with the correlation coefficient（R^2） of 0.981 and cross-validated correlation coefficient（Rcv^2） of 0.967. The established QSAR model has good stability and predictability based on the results from Rcv2 of leave-one-out cross-validation, AIC, FIT and tα/2. The quantum chemical analyses were performed from two aspects of frontier molecular orbital and entropy. The results show that two structural describers are crucial to the bioconcentration activity of chloroanilines.
基金The project supported by a grant from Key Project of Science and Technology of Education Ministry, China (No. 00250) the program of KJCXGC-01, NWNU, China
文摘Contact glow discharge electrolysis of some chloroanilines in sodium sulfate was investigated in different initial concentrations. Each of them underwent the dechlorination, deam-ination through oxidative degradation, and were eventually decomposed into hydrogen carbonate and carbon dioxide. It was testified that the chlorine atom and amidogen could be transformed into chloride ion and nitrite ion, respectively. Fe2+ has a remarkable catalytic effect on the degradation of them. On the basis of the detailed analysis of the intermediate products and kinetic behaviors, the reaction pathway was proposed, in which the attack of hydroxyl radical on the benzene ring of starting material might be a key step.
