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Nitriles as main products from the oxidation of primary amines by ferrate(VI): Kinetics, mechanisms and toxicological implications for nitrogenous disinfection byproduct control
Water Research ( IF 12.8 ) Pub Date : 2021-11-19 , DOI: 10.1016/j.watres.2021.117881
Valentin Rougé 1 , Jaedon Shin 2 , Pham Thi Thai Ha Nguyen 1 , Dong Jang 1 , Woongbae Lee 1 , Beate I Escher 3 , Yunho Lee 1
Affiliation  

Ferrate (Fe(VI)), a promising water treatment oxidant, can be used for micropollutant abatement or disinfection byproduct mitigation. However, knowledge gaps remain concerning the interaction between Fe(VI) and dissolved organic matter structures, notably primary amines. This study investigated degradation kinetics and products of several aliphatic primary amines by Fe(VI). Primary amines showed appreciable reactivity toward Fe(VI) (2.7–68 M−1s−1 at pH 7–9), ranking as follows: benzylamine > phenethylamine > phenylpropylamine > methylamine ≈ propylamine. Nitriles were the main oxidation products of the primary amines, with molar yields of 61–103%. Minor products included aldehydes, carboxylic acids, nitroalkanes, nitrite, nitrate, and ammonia. The buffering conditions were important. Compared to phosphate, borate enhanced the reactivity of the amines and shifted the products from nitriles to carbonyls. An evaluation of the effect potency of some cyano-compounds by an in vitro bioassay for oxidative stress response and cytotoxicity suggested that non-halogenated nitriles are unlikely to pose a significant threat because they were only toxic at high concentrations, acted as baseline toxicants and did not cause oxidative stress, unlike halonitroalkanes or halonitriles. The formation of non-halogenated nitriles is preferable to the formation of nitroalkanes arising from the ozonation of primary amines (other than amino acid N-terminals) because, during chlorination, nitriles remain unreactive while nitroalkanes lead to potent halonitroalkanes.



中文翻译:

高铁酸盐 (VI) 氧化伯胺的主要产物腈:含氮消毒副产物控制的动力学、机制和毒理学意义

高铁酸盐 (Fe(VI)) 是一种很有前途的水处理氧化剂,可用于微量污染物减排或消毒副产物缓解。然而,关于 Fe(VI) 和溶解的有机物质结构,特别是伯胺之间的相互作用,知识差距仍然存在。本研究调查了 Fe(VI) 对几种脂肪族伯胺的降解动力学和产物。伯胺对 Fe(VI) (2.7–68 M -1 s -1pH 7-9),排序如下:苄胺>苯乙胺>苯丙胺>甲胺≈丙胺。腈类是伯胺的主要氧化产物,摩尔产率为 61-103%。次要产物包括醛、羧酸、硝基烷烃、亚硝酸盐、硝酸盐和氨。缓冲条件很重要。与磷酸盐相比,硼酸盐增强了胺的反应性并将产物从腈转化为羰基。通过体外实验评估某些氰基化合物的效力氧化应激反应和细胞毒性的生物测定表明,与卤代硝基烷烃或卤腈不同,非卤化腈类不太可能构成重大威胁,因为它们仅在高浓度时才有毒性,作为基线毒物,不会引起氧化应激。非卤化腈的形成优于由伯胺(氨基酸 N 端除外)臭氧化产生的硝基烷烃的形成,因为在氯化过程中,腈类保持不反应,而硝基烷烃会产生有效的卤代硝基烷烃。

更新日期:2021-11-30
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