Chen Xue Mei, Li Hao-Ran, Feng Xi Lai, Wang Hao-Tong, Sun Xu-Hui
College of Chemical Engineering, Northeast Electric Power University, Jilin City 132012, P. R. China.
ACS Omega. 2022 Jul 13;7(29):24942-24950. doi: 10.1021/acsomega.1c06447. eCollection 2022 Jul 26.
The abiotic reaction products of polycyclic aromatic hydrocarbons (PAHs) with hydroxyl radicals (OH) and nitrate radicals (NO) are nitro-, oxygen-, and hydroxyl-containing PAHs (NPAHs, OPAHs, and OHPAHs). Four methods of the highest occupied molecular orbital (HOMO), Fukui function (FF), dual descriptor (DD), and population of π electrons (PP-π) are selected to predict the chemical reactivity of PAHs attacked by OH and NO in this study. The predicted OH-initiated and NO-initiated transformation products are compared with the main PAH transformation products (PAH-TPs) observed in the laboratory. The results indicate that PP-π and DD approaches fail to predict the transformation products of fused PAHs containing five-membered rings. By predicting the PAH-TPs of 13-14 out of the 15 parent PAHs accurately, HOMO and FF methods were shown to be suitable for predicting the transformation products formed from the abiotic reactions of fused PAHs with OH and NO.
多环芳烃（PAHs）与羟基自由基（OH）和硝酸根自由基（NO）发生的非生物反应产物是含硝基、氧和羟基的多环芳烃（NPAHs、OPAHs和OHPAHs）。本研究选择了最高占据分子轨道（HOMO）、福井函数（FF）、双描述符（DD）和π电子布居（PP-π）这四种方法来预测PAHs被OH和NO攻击时的化学反应活性。将预测的由OH引发和NO引发的转化产物与实验室中观察到的主要PAH转化产物（PAH-TPs）进行比较。结果表明，PP-π和DD方法无法预测含五元环稠合PAHs的转化产物。通过准确预测15种母体PAHs中13 - 14种的PAH-TPs，HOMO和FF方法被证明适用于预测稠合PAHs与OH和NO发生非生物反应形成的转化产物。
