Research Group of Environmental Chemistry, Ecotoxicology & Food Toxicology, Institute of Environmental Sciences & Public Health, University of Gdańsk, Gdańsk, Poland.
J Environ Sci Health A Tox Hazard Subst Environ Eng. 2012;47(2):155-66. doi: 10.1080/10934529.2012.640243.
Polychlorinated trans-azobenzenes (PCt-ABs) are less studied a highly toxic impurity in 2,3-dichloroaniline (2,3-D) and some herbicides and are compounds of environmental relevance lacking experimental physical and chemical properties data. In this study, to fulfill gaps on environmentally relevant partitioning properties of PCABs, the values of water solubility (μg/L and log S) have been determined for 209 congeners of chloro-trans-azobenzene (Ct-AB) by means of quantitative structure - property relationship (QSPR) approach and artificial neural networks (ANN) predictive ability. The quantitative structure - property relationship (QSPR) approach used based on geometry optimalization and quantum-chemical structural descriptors, which were computed on the level of density functional theory (DFT) using B3LYP functional and 6-311++G** basis set in Gaussian 03 and the semi-empirical quantum chemistry method for property parameterization (PM6) in the molecular orbital package (MOPAC) software. The predicted solubility of PCt-ABs by PM6 and DFT models and depending on a congener within a homologue class varied between 1995-11481 and 5370-15135 μg/L for mono-; 170-5495 and 138-9332 μg/L for di-; 36-1950 and 209-5248 μg/L for tri-; 15-794 and 41-3715 μg/L for tetra-; 5.5-209 and 39-1259 μg/L for penta-; 1.8-98 and 3.5-1096 μg/L for hexa-; 1.5-34 and 4.7-214 μg/L for hepta-; 0.71-6.2 and 0.76-26 μg/L for octa-; 0.83-1.7 and 0.69-1.2 μg/L for nonaCt-ABs; and between 0.36 and 0.04 μg/L for decaCt-AB, respectively. The calculations by PM6 were highly efficient and inexpensive compared to these by DFT, while both models gave data of similar accuracy.
多氯代反式偶氮苯（PCt-ABs）是 2,3-二氯苯胺（2,3-D）和一些除草剂中研究较少的一种高毒性杂质，是环境相关的化合物，缺乏实验物理化学性质数据。在这项研究中，为了填补 PCABs 环境相关分配性质的空白，通过定量结构-性质关系（QSPR）方法和人工神经网络（ANN）预测能力，确定了 209 种氯代反式偶氮苯（Ct-AB）同系物的水溶解度（μg/L 和 log S）值。定量结构-性质关系（QSPR）方法基于几何优化和量子化学结构描述符，这些描述符是在密度泛函理论（DFT）水平上使用 B3LYP 函数和 6-311++G** 基组在高斯 03 中计算的，在分子轨道包（MOPAC）软件中的半经验量子化学方法用于性质参数化（PM6）。通过 PM6 和 DFT 模型预测的 PCt-ABs 的溶解度，取决于同系物内的同类物，单氯代物的范围在 1995-11481 和 5370-15135 μg/L 之间；二氯代物的范围在 170-5495 和 138-9332 μg/L 之间；三氯代物的范围在 36-1950 和 209-5248 μg/L 之间；四氯代物的范围在 15-794 和 41-3715 μg/L 之间；五氯代物的范围在 5.5-209 和 39-1259 μg/L 之间；六氯代物的范围在 1.8-98 和 3.5-1096 μg/L 之间；七氯代物的范围在 1.5-34 和 4.7-214 μg/L 之间；八氯代物的范围在 0.71-6.2 和 0.76-26 μg/L 之间；九氯代物的范围在 0.83-1.7 和 0.69-1.2 μg/L 之间；十氯代物的范围在 0.36-0.04 μg/L 之间；十一氯代物的范围在 0.36 和 0.04 μg/L 之间。与 DFT 相比，PM6 的计算效率高且成本低，而两种模型都给出了相似精度的数据。
