Nitroxyl Radical/Copper-Catalyzed Electrooxidation of Alcohols and Amines at Low Potentials
Nitroxyl Radical/Copper-Catalyzed Electrooxidation of Alcohols and Amines at Low Potentials
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DOI：
10.1248/cpb.c21-00409
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发表时间：
2021-10-01
影响因子：
1.7
通讯作者：
Sato, Katsuhiko
中科院分区：
文献类型：
--
作者：
Sugiyama, Kyoko;Sasano, Yusuke;Sato, Katsuhiko
氮氧基，如2，2，6，6-四甲基哌啶N-氧基(TEMPO)可以催化醇和胺的电化学氧化。由于在这个过程中得到的氧化电流取决于醇和胺的浓度，所以这个过程可以应用于对它们的传感。然而，氮氧自由基所需的较高氧化电位会对生物样品中各种还原物质产生干扰氧化电流，从而影响分析物测定的准确性。在这项研究中，我们通过使用氮氧基和铜盐的协同氧化催化，研究了醇和胺在低电位下的电氧化。用比TEMPO催化活性高的去甲托品N-氧基(NNO)作为硝基自由基。在低电位下，氧化电流增大，且这种增大与乙醇浓度有关。在胺的电氧化情况下，在低胺浓度下，氧化电流与胺浓度呈正相关。因此，低电势协同催化可以应用于酒精和胺的电氧化，开发出适合临床环境的准确传感器。
Nitroxyl radicals, such as 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO), can catalyze the electrochemical oxidation of alcohols and amines. Because the oxidation current obtained in this process depends on the concentration of alcohols and amines, this process can be applied to their sensing. However, the relatively high oxidation potentials required by nitroxyl radicals can induce interfering oxidation currents from various reductive substances in biological samples, which affects the accuracy of analyte measurements. In this study, we examined the electrooxidation of alcohols and amines at a low potential by applying cooperative oxidation catalysis using a nitroxyl radical and a copper salt. Nortropine N-oxyl (NNO), which showed higher catalytic activity than TEMPO was used as the nitroxyl radical. An increase in the oxidation current was observed at the low potential, and this increase depended on the alcohol concentration. In the case of the electrooxidation of amines, a positive correlation between oxidation current and amine concentration was observed at low amine concentrations. Therefore, low-potential cooperative catalysis can be applied to alcohol and amine electrooxidation for the development of accurate sensors suitable for clinical settings.