Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine
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 <...
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doaj-bddff88b6e8d49b3ac0ef3a6de44f4c52020-11-24T23:48:13ZengMDPI AGCatalysts2073-43442018-12-0181264910.3390/catal8120649catal8120649Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of LidocaineKatsuhiko Sato0Tetsuya Ono1Yusuke Sasano2Fumiya Sato3Masayuki Kumano4Kentaro Yoshida5Takenori Dairaku6Yoshiharu Iwabuchi7Yoshitomo Kashiwagi8Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, JapanSchool of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, JapanGraduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, JapanGraduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, JapanGraduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, JapanSchool of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, JapanSchool of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, JapanGraduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, JapanSchool of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, JapanThe 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 <i>N</i>-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 <i>tert</i>-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.https://www.mdpi.com/2073-4344/8/12/649sensornitroxyl radicalelectrocatalytic oxidationlidocaineTEMPO |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Katsuhiko Sato Tetsuya Ono Yusuke Sasano Fumiya Sato Masayuki Kumano Kentaro Yoshida Takenori Dairaku Yoshiharu Iwabuchi Yoshitomo Kashiwagi |
spellingShingle |
Katsuhiko Sato Tetsuya Ono Yusuke Sasano Fumiya Sato Masayuki Kumano Kentaro Yoshida Takenori Dairaku Yoshiharu Iwabuchi Yoshitomo Kashiwagi Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine Catalysts sensor nitroxyl radical electrocatalytic oxidation lidocaine TEMPO |
author_facet |
Katsuhiko Sato Tetsuya Ono Yusuke Sasano Fumiya Sato Masayuki Kumano Kentaro Yoshida Takenori Dairaku Yoshiharu Iwabuchi Yoshitomo Kashiwagi |
author_sort |
Katsuhiko Sato |
title |
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine |
title_short |
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine |
title_full |
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine |
title_fullStr |
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine |
title_full_unstemmed |
Electrochemical Oxidation of Amines Using a Nitroxyl Radical Catalyst and the Electroanalysis of Lidocaine |
title_sort |
electrochemical oxidation of amines using a nitroxyl radical catalyst and the electroanalysis of lidocaine |
publisher |
MDPI AG |
series |
Catalysts |
issn |
2073-4344 |
publishDate |
2018-12-01 |
description |
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 <i>N</i>-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 <i>tert</i>-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. |
topic |
sensor nitroxyl radical electrocatalytic oxidation lidocaine TEMPO |
url |
https://www.mdpi.com/2073-4344/8/12/649 |
work_keys_str_mv |
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1725486655151800320 |