Zhu Huicen, Guo Weimin, Shen Zhemin, Tang Qingli, Ji Wenchao, Jia Lijuan
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Chemosphere. 2015 Jan;119:65-71. doi: 10.1016/j.chemosphere.2014.05.068. Epub 2014 Jun 24.
Although some researches about the degradation of organic pollutants have been carried out during recent years, reaction rate constants are available only for homologue compounds with similar structures or components. Therefore, it is of great significance to find a universal relationship between reaction rate and certain parameters of several diverse organic pollutants. In this study, removal ratio and kinetics of 33 kinds of organic substances were investigated by ozonation process, including azo dyes, heterocyclic compounds, ionic compounds and so on. Most quantum chemical parameters were conducted by using Gaussian 09 at the DFT B3LYP/6-311G level, including μ, q H(+), q(C)minq(C)max, ELUMO and EHOMO. Other descriptors, bond order (BO) as well as Fukui indices (f(+), f(-) and f(0)), were calculated by Material Studio 6.1 at Dmol(3)/GGA-BLYP/DNP(3.5) basis for each organic compound. The recommended model for predicting rate constants was lnk'=1.978-95.484f(0)x-3.350q(C)min+38.221f(+)x, which had the squared regression coefficient R(2)=0.763 and standard deviation SD=0.716. The results of t test and the Fisher test suggested that the model exhibited optimum stability. Also, the model was validated by internal and external validations. Recommended QSAR model showed that the highest f(0) value of main-chain carbons (f(0)x) is more closely related to lnk' than other quantum descriptors.
尽管近年来已经开展了一些关于有机污染物降解的研究，但反应速率常数仅适用于结构或成分相似的同系物化合物。因此，找到几种不同有机污染物的反应速率与某些参数之间的普遍关系具有重要意义。在本研究中，通过臭氧化过程研究了33种有机物质的去除率和动力学，包括偶氮染料、杂环化合物、离子化合物等。大多数量子化学参数是在DFT B3LYP/6-311G水平上使用Gaussian 09进行计算的，包括μ、q H(+)、q(C)minq(C)max、ELUMO和EHOMO。其他描述符，键级(BO)以及福井指数(f(+)、f(-)和f(0))，是通过Material Studio 6.1在Dmol(3)/GGA-BLYP/DNP(3.5)基组下对每种有机化合物进行计算的。推荐的预测速率常数的模型为lnk'=1.978-95.484f(0)x-3.350q(C)min+38.221f(+)x，其平方回归系数R(2)=0.763，标准差SD=0.716。t检验和Fisher检验的结果表明该模型具有最佳稳定性。此外，该模型通过内部和外部验证进行了验证。推荐的QSAR模型表明，主链碳的最高f(0)值(f(0)x)与lnk'的关系比其他量子描述符更密切。
