Electrochemically assisted Fenton reaction: reaction of hydroxyl radicals with xenobiotics followed by on-line analysis with high-performance liquid chromatography/tandem mass spectrometry

Autor: Jurva, U, Wikstrom, H V, Bruins, A P
Přispěvatelé: Medicinal Chemistry, Pharmaceutical Analysis
Jazyk: angličtina
Rok vydání: 2002
Předmět:
Zdroj: Rapid Communications in Mass Spectrometry, 16(20), 1934-1940. Wiley
ISSN: 0951-4198
Popis: Oxygen radicals are generated in vivo by various processes, often as toxic intermediates in different metabolic transformations, and have been shown to play an important role for a large number of diseases. In this article we introduce an electrochemical flow-through system that allows generation of hydroxyl radicals for reaction with xenobiotics and subsequent detection of the oxidation products on-line with high-performance liquid chromatography/tandem mass spectrometry (HPLC/NIS/MS). The system is based on the Fenton reaction and is predominantly aimed at the generation of hydroxyl radicals; however, by minor variations to the system, a broad range of other radicals can be produced. Optimization of the system was performed with the radical scavenger 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Under the same physical conditions, one injection through the electrochemical cell gave a higher yield of the oxidation product N-hydroxy-5,5-dimethylpyrrolidin-2-one than what was attained after 60 min with a chemical Fenton system catalyzed by ascorbic acid. Since the iron is added as Fe3+ the initial mixture is 'inactive' until it reaches the electrochemical cell. This makes it very suitable for on-line analysis of the generated compounds, since the whole reaction mixture, including substrate, can be kept in a vial in an autosampler. The system described provides a useful tool for investigation of new radical scavengers and antioxidants. Since the hydroxyl radical adds readily to unsaturated pi-systems, the technique is also suitable for on-line generation and characterization of potential drug metabolites resulting from hydroxylation of double bonds and aromatic systems. Copyright (C) 2002 John Wiley Sons, Ltd.
Databáze: OpenAIRE
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