N-nitration of secondary aliphatic amines in the particle phase.
N-nitration of secondary aliphatic amines in the particle phase.
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DOI：
10.1016/j.chemosphere.2022.133639
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发表时间：
2022-01
期刊：
影响因子：
8.8
通讯作者：
Tianzeng Chen;Y. Ge;Yongchun Liu;Hong S. He
中科院分区：
文献类型：
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作者：
Tianzeng Chen;Y. Ge;Yongchun Liu;Hong S. He
胺经常在大气颗粒中检测到，并与其他颗粒相成分在内部混合。然而，对于胺进入颗粒相后与活性物质进一步反应的研究仍然有限。本研究研究了 DMA 与 (NH4)2SO4 之间的取代反应形成的颗粒二甲胺 (DMA) 与 NOx 的硝化反应过程。原位衰减全反射红外傅里叶变换光谱 (in situATR-FTIR) 和质子转移反应质谱 (PTR-MS) 以及使用 6–311++G (d, p) 基组的 B3LYP 水平的 DFT 方法主要用于证实DMA的硝化/亚硝化过程中形成硝胺和亚硝胺。当颗粒 DMA 与 NO2 反应时，首先形成氢键中间体 ([(CH3)2N⋯HONO])，随后形成氨基自由基，然后分别通过与 NO2 和 NO 的加成反应形成硝基胺和亚硝基胺。 NO2的二聚体（即N2O4）以及NO和NO2的产物（即N2O3）也可以与DMA反应，攻击DMA中心N原子上的孤对电子，最终形成硝基和亚硝基胺。该研究有助于揭示有机胺在颗粒相中的硝化反应机理。它还有助于了解大气中氮循环的过程。
Amines are frequently detected in atmospheric particles and are internally mixed with other particle-phase components. However, research on the further reactions of amine with reactive species after entering the particle phase is still limited. This study investigated the nitration reaction process of particulate dimethylamine (DMA), formed via a substitution reaction between DMA and (NH4)2SO4, with NOx.In situattenuated total reflectance-infrared Fourier transform spectroscopy (in situATR-FTIR) and proton transfer reaction mass spectroscopy (PTR-MS), as well as DFT methods at the B3LYP level using the 6–311++G (d, p) basis set, were mainly used to confirm the formation of nitramine and nitrosamine in the nitration/nitrosation process of DMA. A hydrogen-bonding intermediate ([(CH3)2N⋯HONO]) is initially formed when particulate DMA reacts with NO2followed by aminyl radical formation, and then nitr- and nitros-amine form through addition reactions with NO2and NO, respectively. The dimer of NO2(i.e., N2O4) and the product of NO and NO2(i.e., N2O3) can also react with DMA to attack the lone pair electrons on the central N atom of DMA to finally form nitr- and nitros-amine. This study helps reveal the nitration reaction mechanism of organic amines in the particle phase. It also aids in understanding the process of nitrogen cycling in the atmosphere.