Generation of Iron(IV) in the Oxidation of Amines by Ferrate(VI): Theoretical Insight and Implications in Oxidizing Pharmaceuticals
Generation of Iron(IV) in the Oxidation of Amines by Ferrate(VI): Theoretical Insight and Implications in Oxidizing Pharmaceuticals
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DOI：
10.1021/acsestwater.1c00156
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发表时间：
2021-07-27
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影响因子：
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通讯作者：
Sharma, Virender K.
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作者：
Baum, J. Clayton;Feng, Mingbao;Sharma, Virender K.
脂肪族胺广泛存在于天然沃茨中，是溶解有机物和水中微污染物（如药物）的主要组成部分之一。研究了脂肪胺{一甲胺（CH 3 NH 2，MMA）、二甲胺[（CH 3）（2）NH，DMA]和三甲胺[（CH 3）（3）N，TMA] }对高铁酸盐[（FeO 42-）-O-VI，Fe（VI）]氧化药物（甲氧苄啶、阿替洛尔、卡马西平和磺胺嘧啶）的作用。增强的幅度随胺而变化，DMA显示出最大的潜力，以增加甲氧苄啶的氧化水平。的计算方法被施加到描述的趋势，增加的氧化水平的Fe（VI）在胺的存在下。计算表明，Fe（VI）/胺溶液形成高反应性的Fe-IV物种作为中间体，与药物反应以产生增强的氧化。在Fe（VI）与胺TS 1反应的速率决定步骤中，Fe（VI）被还原并从N中提取H，然后将O原子转移到N中以形成涉及氮氧自由基的非常稳定的中间体。然后将提取的H转移回TS 2中的N-O基团以形成H键合的产物复合物，其解离为产物。Fe-IV物质与胺类型的反应性的差异解释了实验中观察到的药物氧化增强的趋势。
Aliphatic amines are ubiquitously present in natural waters and constitute one of the major moieties in dissolved organic matter and water micropollutants such as pharmaceuticals. This paper presents aliphatic amine {monomethylamine (CH3NH2, MMA), dimethylamine [(CH3)(2)NH, DMA], and trimethylamine [(CH3)(3)N, TMA] }-enhanced oxidation of pharmaceuticals (trimethoprim, atenolol, carbamazepine, and sulfadiazine) by ferrate(VI) [(FeO42-)-O-VI, Fe(VI)]. The magnitude of the enhancement varies with amines, and DMA shows the greatest potential to increase the level of oxidation of trimethoprim. The computational approach is applied to describe the trend of an increased level of oxidation by Fe(VI) in the presence of amines. The computation showed that an Fe(VI)/amine solution forms highly reactive Fe-IV species as intermediates that react with pharmaceuticals to yield enhanced oxidation. In the rate-determining step of Fe(VI) reactions with amines, TS1, the Fe(VI) is reduced and abstracts an H from N, followed by the transfer of an O atom to N to form a very stable intermediate involving a nitroxide radical. The abstracted H is then transferred back to the N-O group in TS2 to form an H-bonded product complex, which dissociates to the products. The difference in the reactivity of the Fe-IV species with the type of amine explains the trend seen experimentally in the enhanced oxidation of pharmaceuticals.