Department of Civil Engineering, University of Minnesota, 500 Pillsbury Dr. SE, Minneapolis, MN 55455, USA.
Environ Sci Process Impacts. 2014 Apr;16(4):832-8. doi: 10.1039/c3em00479a.
Photo-generated transient species, such as the carbonate radical and triplet excited state natural organic matter, mediate the oxidation of pollutants in various sunlit or artificially irradiated systems. In this work, one-electron oxidation potentials for 70 nitrogen-containing compounds were computed, and literature data were used to develop quantitative structure-activity relationships (QSARs) for prediction of the second order reaction rate constants with these two oxidants. For carbonate radical, separate QSARs were necessary for compounds with and without resonance stabilization of the resulting radical, and predicted rate constants were, on average, within a factor of three of experimental values. With the limited data set available, results suggest that one-electron oxidation potential is also a viable descriptor variable for predictions of rate constants with triplet excited states.
光生瞬变物种，如碳酸盐自由基和三重态激发态天然有机物，介导各种阳光照射或人工辐照系统中污染物的氧化。在这项工作中，计算了 70 种含氮化合物的单电子氧化电势，并利用文献数据开发了定量结构-活性关系（QSAR），用于预测这两种氧化剂与化合物的二级反应速率常数。对于碳酸盐自由基，对于没有和有自由基共振稳定化的化合物，需要分别建立 QSAR，预测的速率常数平均在实验值的三倍以内。在所获得的有限数据集的基础上，结果表明，单电子氧化电势也是预测与三重态激发态化合物的速率常数的可行描述符变量。
