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Updated: May 26, 2026

Analysis of Volatile and Oxidation Sensitive Compounds Using a Cold Inlet System and Electron Impact Mass Spectrometry
Published on: September 5, 2014
Product analysis of caffeic acid oxidation by on-line electrochemistry/electrospray ionization mass spectrometry
Ryuichi Arakawa1, Masashi Yamaguchi, Hiroki Hotta
1Department of Applied Chemistry, Kansai University, Osaka, Japan. arak@ipcku.kansai-u.ac.jp
Abstract:
On-line electrochemistry/electrospray ionization mass spectrometry (EC/ESI-MS) was developed using a microflow electrolytic cell. This technique was applied to electrochemical oxidation of caffeic acid (CAF) which is known to be a highly antioxidative agent. Effects of electrolytic potentials on ion intensities of product ions and on electrolytic currents were examined at different pHs. Dimer products were detected at electrolytic potentials of E = 0.7 V (vs. Ag/AgCl) and trimer products at 1.0 V at pH 9. Dimer products were distinguished from hydrogen-bonded complexes by MS/MS experiments. Hydrogen/deuterium exchange experiments determined the number of hydroxyl and carboxyl groups in the Dimers formed by electrolysis. The mechanism of oxidative polymerization of CAF is discussed with speculation as to the structure of the dimer product.
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