Amatore Christian, Arbault Stéphane, Ducrocq Claire, Hu Shenghua, Tapsoba Issa
Ecole Normale Supérieure, Département de Chimie, UMR CNRS-ENS-UPMC 8640 Pasteur, 24 rue Lhomond, 75231 Paris Cedex 05, France.
ChemMedChem. 2007 Jun;2(6):898-903. doi: 10.1002/cmdc.200700016.
Under physiological conditions, it is usually accepted that the aerobic decomposition of Angeli's salt produces nitrite (NO(2)(-)) and nitroxyl (HNO), which dimerizes and leads to N(2)O. No consensus has yet been established on the formation of nitric oxide (NO) and/or peroxynitrite (ONOO(-)) by Angeli's salt. Because this salt has recently been shown to have pharmacological properties for the treatment of cardiovascular diseases, identification of its follow-up reactive intermediates is of increasing importance. In this work, we investigated the decomposition mechanism of Angeli's salt by voltammetry performed at platinized carbon fiber microelectrodes. By following the decomposition process of Angeli's salt, we showed that the mechanism depends on the experimental conditions. Under aerobic neutral and slightly alkaline conditions, the formation of HNO, NO(2)(-), but also of nitric oxide NO was demonstrated. In strongly alkaline buffer (pH>10), we observed the formation of peroxynitrite ONOO(-) in the presence of oxygen. These electrochemical results are supported by comparison with UV spectrophotometry data.
在生理条件下,通常认为安吉利盐的有氧分解会产生亚硝酸盐(NO₂⁻)和硝酰(HNO),后者二聚化并生成N₂O。关于安吉利盐是否会形成一氧化氮(NO)和/或过氧亚硝酸盐(ONOO⁻),目前尚未达成共识。由于这种盐最近已被证明具有治疗心血管疾病的药理特性,因此确定其后续反应中间体变得越来越重要。在这项工作中,我们通过在镀铂碳纤维微电极上进行伏安法研究了安吉利盐的分解机制。通过跟踪安吉利盐的分解过程,我们发现其机制取决于实验条件。在有氧的中性和微碱性条件下,证明了HNO、NO₂⁻以及一氧化氮NO的形成。在强碱性缓冲液(pH>10)中,我们观察到在有氧气存在的情况下会形成过氧亚硝酸盐ONOO⁻。这些电化学结果通过与紫外分光光度法数据进行比较得到了支持。