Online H/D exchange liquid chromatography as a support for the mass spectrometric identification of the oxidation products of melatonin

The hydrogen-deuterium exchange of protonated melatonin and its in vitro oxidation end-products have been examined by liquid chromatography coupled with ion-trap mass spectrometry. Specific H/D scrambling of protons in the C2 and C4 positions of the indole ring during gas-phase fragmentation process...

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Bibliographic Details
Published in:Journal of mass spectrometry. 2009-03, Vol.44 (3), p.318-329
Main Authors: Collin, Fabrice, Bonnefont-Rousselot, Dominique, Yous, Saï, Marchetti, Catherine, Jore, Daniel, Gardès-Albert, Monique
Format: Article
Language:English
Subjects:
Analytical chemistry
Chemistry
Chromatographic methods and physical methods associated with chromatography
Chromatography, High Pressure Liquid
deuterium exchange
Deuterium Exchange Measurement
Exact sciences and technology
hydroxyl radicals
Kynuramine - analogs & derivatives
Kynuramine - chemistry
Kynuramine - metabolism
liquid chromatography
Mass Spectrometry
melatonin
Melatonin - analogs & derivatives
Melatonin - chemistry
Melatonin - metabolism
Models, Molecular
Other chromatographic methods
oxidation
Oxidation-Reduction
Reactive Oxygen Species - chemistry
Reactive Oxygen Species - metabolism
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Summary:The hydrogen-deuterium exchange of protonated melatonin and its in vitro oxidation end-products have been examined by liquid chromatography coupled with ion-trap mass spectrometry. Specific H/D scrambling of protons in the C2 and C4 positions of the indole ring during gas-phase fragmentation process was observed for both melatonin and its oxidation products. Collision-induced dissociation spectra showed losses of variably deuterated NH₃, H₂O and CH₃CONH₂. In addition, a similar H/D scrambling behaviour was observed for the oxidation products, obtained from the opening of the indole ring by oxidative attack. Fragmentation pathways are proposed and H/D scrambling has been employed as a fingerprint, allowing identification of N¹-acetyl-5-methoxykynurenin (AMK), N¹-acetyl-N²-formyl-5-methoxykynurenin (AFMK), dehydro-AFMK and hydroxymelatonin as the oxidation products of melatonin in vitro. Copyright © 2008 John Wiley & Sons, Ltd.
ISSN:1076-5174
1096-9888
DOI:10.1002/jms.1508