Ono Tetsuya
The School of Pharmaceutical Sciences, Ohu University.
Yakugaku Zasshi. 2023;143(2):95-100. doi: 10.1248/yakushi.22-00143.
Organic nitroxyl radicals represented by 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) are known to be compounds that catalyze alcohol oxidation reactions. These catalytic reactions can be applied to a wide range of compounds with hydroxy and amino groups. It is also possible to selectively oxidize primary alcohols by designing the skeleton around the nitroxyl radical moiety for use in organic synthesis. Reactions can also be carried out by electrochemical methods, and the electrical current measured during the reaction can be used to quantify the substrates. Therefore, the combination of reactions catalyzed by nitroxyl radicals and electrochemical techniques is expected to be applied as a new analytical method. However, since the reaction does not proceed rapidly in neutral aqueous solutions, it has mostly been applied in basic aqueous solutions or organic solvents, and there have been no reports on sensor applications under physiological conditions. Herein, we have developed a novel catalyst, nortropine N-oxyl (NNO), which is highly active even in neutral aqueous solutions, and have found that it can be used for the analysis of biological components and drugs under physiological conditions. The combination of this method with enzymatic reactions made it possible to specifically detect certain compounds. In this review, we describe a novel analytical method that combines these nitroxyl radicals with electrochemical methods.
以2,2,6,6-四甲基哌啶-1-氧基（TEMPO）为代表的有机硝酰自由基是已知的催化醇氧化反应的化合物。这些催化反应可应用于广泛的含羟基和氨基的化合物。通过设计硝酰自由基部分周围的骨架用于有机合成，也可以选择性地氧化伯醇。反应也可以通过电化学方法进行，反应过程中测量的电流可用于定量底物。因此，硝酰自由基催化的反应与电化学技术的结合有望作为一种新的分析方法应用。然而，由于该反应在中性水溶液中进行得并不迅速，它大多应用于碱性水溶液或有机溶剂中，且尚无关于生理条件下传感器应用的报道。在此，我们开发了一种新型催化剂，去甲托品N-氧基（NNO），它即使在中性水溶液中也具有高活性，并且发现它可用于生理条件下生物成分和药物的分析。该方法与酶促反应相结合使得特异性检测某些化合物成为可能。在这篇综述中，我们描述了一种将这些硝酰自由基与电化学方法相结合的新型分析方法。
