Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine
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DOI：
10.3390/catal8120649
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发表时间：
2018-12
期刊：
影响因子：
3.9
通讯作者：
Katsuhiko Sato;Tetsuya Ono;Y. Sasano;F. Sato;Masayuki Kumano;Kentaro Yoshida;Takenori Dairaku;
中科院分区：
文献类型：
--
作者：
Katsuhiko Sato;Tetsuya Ono;Y. Sasano;F. Sato;Masayuki Kumano;Kentaro Yoshida;Takenori Dairaku;
2,2,6,6-四甲基哌啶1-氧基（TEMPO）的硝酰基不仅可以电氧化醇，还可以电氧化胺。然而，由于活性位点硝酰基周围存在较大的空间位阻，TEMPO 在中性水溶液中活性较低。因此，合成了去甲托品N-氧基（NNO）来提高TEMPO的催化能力，并研究阳极电流变化对胺类的电解氧化作用。研究了乙胺、二乙胺、三乙胺、四乙胺、异丙胺和叔丁胺。结果表明，TEMPO在生理条件下对任何胺均不产生响应电流；然而，NNO确实起到了二乙胺、三乙胺和异丙胺电解氧化催化剂的作用。阳极电流取决于胺浓度，这表明 NNO 可用作胺化合物的电化学传感器。此外，使用校准曲线为 0.1-10 mM 的 NNO 演示了利多卡因（一种含有叔胺结构的局部麻醉剂）的电化学检测。
The nitroxyl radical of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) can electro-oxidize not only alcohols but also amines. However, TEMPO has low activity in a neutral aqueous solution due to the large steric hindrance around the nitroxyl radical, which is the active site. Therefore, nortropine N-oxyl (NNO) was synthesized to improve the catalytic ability of TEMPO and to investigate the electrolytic oxidation effect on amines from anodic current changes. Ethylamine, diethylamine, triethylamine, tetraethylamine, isopropylamine, and tert-butylamine were investigated. The results indicated that TEMPO produced no response current for any of the amines under physiological conditions; however, NNO did function as an electrolytic oxidation catalyst for diethylamine, triethylamine, and isopropylamine. The anodic current depended on amine concentration, which suggests that NNO can be used as an electrochemical sensor for amine compounds. In addition, electrochemical detection of lidocaine, a local anesthetic containing a tertiary amine structure, was demonstrated using NNO with a calibration curve of 0.1–10 mM.