CNRS, Chimie et Interdisciplinarité: Synthèse, Analyse et Modélisation (CEISAM), UMR 6230, LUNAM Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322, Nantes Cedex 3, France.
Anal Bioanal Chem. 2013 Jul;405(17):5817-24. doi: 10.1007/s00216-013-6977-z. Epub 2013 May 15.
In situ NMR spectroelectrochemistry is presented in this study as a useful hybrid technique for the chemical structure elucidation of unstable intermediate species. An experimental setting was designed to follow the reaction in real time during the experimental electrochemical process. The analysis of (1)H NMR spectra recorded in situ permitted us (1) to elucidate the reaction pathway of the electrochemical oxidation of phenacetin and (2) to reveal the quinone imine as a reactive intermediate species without using any trapping reaction. Phenacetin has been considered as hepatotoxic at high therapeutic amounts, which is why it was chosen as a model to prove the applicability of the analytical method. The use of 1D and 2D NMR experiments led to the elucidation of the major species produced from the oxidation process. We demonstrated that in situ NMR spectroelectrochemistry constitutes a fast way for monitoring unstable quinone imines and elucidating their chemical structures.
本研究提出了原位 NMR 光谱电化学，作为一种有用的混合技术，用于阐明不稳定中间物种的化学结构。设计了一个实验装置，以便在实验电化学过程中实时跟踪反应。对原位记录的 (1)H NMR 谱进行分析，使我们（1）阐明了非那西汀电化学氧化的反应途径，（2）揭示了醌亚胺作为一个反应性中间物种，而无需使用任何捕获反应。非那西汀在高治疗剂量下被认为具有肝毒性，这就是为什么选择它作为模型来证明分析方法的适用性。使用 1D 和 2D NMR 实验，阐明了氧化过程中产生的主要物质。我们证明了原位 NMR 光谱电化学是一种快速监测不稳定醌亚胺并阐明其化学结构的方法。
