The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-poly...The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-polychlorinated biphenyls(PCBs), polychlorinated dibenzodioxins and dibenzofurans(PCDDs and PCDFs). For each compound, five quantum parameters were calculated using AM1 semiempirical molecular orbital methods and used as structure descriptors: average molecular polarizability(α), energy of the lowest unoccupied molecular orbit( E _ LUMO ), energy of the highest occupied molecular orbit( E _ HOMO ), the most positive charge on a hydrogen atom( q _+), and the most negative atomic partial charge( q _-) in the solute molecule. Then standard independent variables in TLSER equation was extracted and two series of quantitative equations between these quantum parameters and aqueous solubility and n -octanol/water partition coefficient were obtained by stepwise multiple linear regression(MLR) method. The developed equations have both quite high accuracy and explicit meanings. And the cross-validation test illustrated the good predictive power and stability of the established models. The results showed that TLSER could be used as a promising approach in the estimation of partition and solubility properties of macromolecular chemicals, such as persistent organic pollutants.展开更多
Based on quantum chemical calculations, TLSER model(theoretical linear solvation energy relationships) and atomic charge approach were applied to model the partition properties(water solubility and octanol/water parti...Based on quantum chemical calculations, TLSER model(theoretical linear solvation energy relationships) and atomic charge approach were applied to model the partition properties(water solubility and octanol/water partition coefficient) of 96 aromatic sulfur-containing carboxylates, including phenylthio, phenylsulfinyl and phenylsulfonyl carboxylates. In comparison with TLSER models, the atomic charge models are more accurate and reliable to predict the partition properties of the kind of compounds. For the atomic charge models, the molecular descriptors are molecular surface area(S), molecular shape(O), weight(M W), net charges on carboxyl group(Q OC), net charges of nitrogen atoms(Q N), and the most negative atomic charge(q -) of the solute molecule. For water solubility(log S W) and octanol/water partition coefficient(log K OW), the correction coefficients r 2 adj(adjusted for degrees of freedom) are 0.936 and 0.938, and the standard deviations are 0.364 and 0.223, respectively.展开更多
通过搜集25个多环芳香烃(PAHs)和84个多氯联苯(PCBs)在聚二甲基硅氧烷(PDMS)上平衡分配系数(log K PDMS-W)的实测值,应用理论线性溶解能关系(TLSER),利用逐步多元线性回归(MLR)方法构建了预测分配系数模型.结果表明:模型具有良好的拟合...通过搜集25个多环芳香烃(PAHs)和84个多氯联苯(PCBs)在聚二甲基硅氧烷(PDMS)上平衡分配系数(log K PDMS-W)的实测值,应用理论线性溶解能关系(TLSER),利用逐步多元线性回归(MLR)方法构建了预测分配系数模型.结果表明:模型具有良好的拟合度(决定系数R 2 adj=0.916)、稳健性(交叉验证系数Q^2 LOO=0.910)和预测能力(外部验证系数Q^2 ext=0.862).同时,模型具有较小的RMSE值(0.264),训练集和验证集中化合物的标准残差|δ|≤3,且杠杆值均小于警戒值h^*(0.103).与前人预测模型相比,该模型具有较少的参数和更加丰富的数据集(109种),化合物的实测值跨度大,应用域也更加广泛,且针对PCBs和PAHs两类化合物有较高的预测精度.因此,本模型可适用于预测在应用域范围内其他与这两类化合物结构相似的有机污染物的K PDMS-W值.展开更多
On the basis of the theoretical linear solvation energy relationship(TLSER) suggested by Wilson et al.and the quantum chemical descriptors computed by AM1 Hamiltonian,a predicting model was developed to characterize t...On the basis of the theoretical linear solvation energy relationship(TLSER) suggested by Wilson et al.and the quantum chemical descriptors computed by AM1 Hamiltonian,a predicting model was developed to characterize the activity coefficients at infinite dilution γi∞ of 34 organic solutes in ionic liquids(ILs) 1-butyl-3-methylimidazolium trifluoromethanesulfonate(BMIMCF3SO3) and 1-propyl-2,3-di-methylimidazolium tetrafluoroborate(PDMIMBF4) at 323.15 K.The results showed that the model had an good correlation and could successfully describe γi∞.In addition,correlation parameters are analyzed to understand the interactions that affect infinite dilution activity coefficients.展开更多
基金TheNationalKeyBasicResearchFoundationofChina (No .G1 9990 4 571 1 )
文摘The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-polychlorinated biphenyls(PCBs), polychlorinated dibenzodioxins and dibenzofurans(PCDDs and PCDFs). For each compound, five quantum parameters were calculated using AM1 semiempirical molecular orbital methods and used as structure descriptors: average molecular polarizability(α), energy of the lowest unoccupied molecular orbit( E _ LUMO ), energy of the highest occupied molecular orbit( E _ HOMO ), the most positive charge on a hydrogen atom( q _+), and the most negative atomic partial charge( q _-) in the solute molecule. Then standard independent variables in TLSER equation was extracted and two series of quantitative equations between these quantum parameters and aqueous solubility and n -octanol/water partition coefficient were obtained by stepwise multiple linear regression(MLR) method. The developed equations have both quite high accuracy and explicit meanings. And the cross-validation test illustrated the good predictive power and stability of the established models. The results showed that TLSER could be used as a promising approach in the estimation of partition and solubility properties of macromolecular chemicals, such as persistent organic pollutants.
文摘Based on quantum chemical calculations, TLSER model(theoretical linear solvation energy relationships) and atomic charge approach were applied to model the partition properties(water solubility and octanol/water partition coefficient) of 96 aromatic sulfur-containing carboxylates, including phenylthio, phenylsulfinyl and phenylsulfonyl carboxylates. In comparison with TLSER models, the atomic charge models are more accurate and reliable to predict the partition properties of the kind of compounds. For the atomic charge models, the molecular descriptors are molecular surface area(S), molecular shape(O), weight(M W), net charges on carboxyl group(Q OC), net charges of nitrogen atoms(Q N), and the most negative atomic charge(q -) of the solute molecule. For water solubility(log S W) and octanol/water partition coefficient(log K OW), the correction coefficients r 2 adj(adjusted for degrees of freedom) are 0.936 and 0.938, and the standard deviations are 0.364 and 0.223, respectively.
基金Supported by the Beijing Municipal Training Programme for the Excellent Talents(Grant No.20081D0500500140)
文摘On the basis of the theoretical linear solvation energy relationship(TLSER) suggested by Wilson et al.and the quantum chemical descriptors computed by AM1 Hamiltonian,a predicting model was developed to characterize the activity coefficients at infinite dilution γi∞ of 34 organic solutes in ionic liquids(ILs) 1-butyl-3-methylimidazolium trifluoromethanesulfonate(BMIMCF3SO3) and 1-propyl-2,3-di-methylimidazolium tetrafluoroborate(PDMIMBF4) at 323.15 K.The results showed that the model had an good correlation and could successfully describe γi∞.In addition,correlation parameters are analyzed to understand the interactions that affect infinite dilution activity coefficients.
