Huang Jun, Yu Gang, Zhang Zu-lin, Wang Yi-lei, Zhu Wei-hua, Wu Guo-shi
Department of Environmental Science and Engineering, POPs Research Center, Tsinghua University, Beijing 100084, China.
J Environ Sci (China). 2004;16(1):21-9.
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(alpha), 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.
采用理论线性溶剂化能关系(TLSER)方法预测了三类对环境具有重要意义的化学品——多氯联苯(PCBs)、多氯二苯并二恶英和多氯二苯并呋喃(PCDDs和PCDFs)的水溶性和正辛醇/水分配系数。对于每种化合物,使用AM1半经验分子轨道方法计算了五个量子参数,并将其用作结构描述符:平均分子极化率(α)、最低未占分子轨道能量(E(LUMO))、最高占据分子轨道能量(E(HOMO))、溶质分子中氢原子上的最大正电荷(q+)以及最负的原子部分电荷(q-)。然后提取TLSER方程中的标准自变量,并通过逐步多元线性回归(MLR)方法获得了这些量子参数与水溶性和正辛醇/水分配系数之间的两个系列定量方程。所建立的方程具有相当高的精度和明确的意义。交叉验证测试表明所建立模型具有良好的预测能力和稳定性。结果表明,TLSER可作为一种有前景的方法用于估算大分子化学品(如持久性有机污染物)的分配和溶解性性质。