Environment Research Institute, Shandong University, Qingdao 266237, China.
Int J Mol Sci. 2023 Feb 8;24(4):3355. doi: 10.3390/ijms24043355.
Criegee intermediates (CIs) are important zwitterionic oxidants in the atmosphere, which affect the budget of OH radicals, amines, alcohols, organic/inorganic acids, etc. In this study, quantum chemical calculation and Born-Oppenheimer molecular dynamic (BOMD) simulation were performed to show the reaction mechanisms of C2 CIs with glycolic acid sulfate (GAS) at the gas-phase and gas-liquid interface, respectively. The results indicate that CIs can react with COOH and OSOH groups of GAS and generate hydroperoxide products. Intramolecular proton transfer reactions occurred in the simulations. Moreover, GAS acts as a proton donor and participates in the hydration of CIs, during which the intramolecular proton transfer also occurs. As GAS widely exists in atmospheric particulate matter, the reaction with GAS is one of the sink pathways of CIs in areas polluted by particulate matter.
Criegee 中间体 (CIs) 是大气中重要的两性离子氧化剂，它们影响 OH 自由基、胺、醇、有机/无机酸等的收支平衡。在这项研究中，通过量子化学计算和 Born-Oppenheimer 分子动力学 (BOMD) 模拟，分别展示了 C2 CIs 在气相和气液界面上与硫酸乙二酸酯 (GAS) 的反应机制。结果表明，CIs 可以与 GAS 的 COOH 和 OSOH 基团反应，生成过氧化物产物。模拟中发生了分子内质子转移反应。此外，GAS 作为质子供体参与 CIs 的水合作用，在此过程中也发生了分子内质子转移。由于 GAS 广泛存在于大气颗粒物中，因此与 GAS 的反应是 CIs 在颗粒物污染地区的一种消耗途径。
