An electron spin resonance study of a novel radical cation produced during the horseradish peroxidase-catalyzed oxidation of tetramethylhydrazine

The one-electron oxidation of tetramethylhydrazine by the horseradish peroxidase/hydrogen peroxide system forms a novel stable radical cation. The steady-state concentration of the tetramethylhydrazine radical cation increases with the hydrazine concentration, but depends on neither the enzyme conce...

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Veröffentlicht in:Biochemical and biophysical research communications 1982-03, Vol.105 (1), p.217-224
Hauptverfasser: Kalyanaraman, B., Mason, Ronald P., Sivarajah, K.
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container_title Biochemical and biophysical research communications
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creator Kalyanaraman, B.
Mason, Ronald P.
Sivarajah, K.
description The one-electron oxidation of tetramethylhydrazine by the horseradish peroxidase/hydrogen peroxide system forms a novel stable radical cation. The steady-state concentration of the tetramethylhydrazine radical cation increases with the hydrazine concentration, but depends on neither the enzyme concentration nor the hydrogen peroxide concentration. A mechanism involving the enzymatic one-electron oxidation of the tetramethylhydrazine radical cation to a dication is proposed to account for the enzyme independency. Incubations containing horseradish peroxidase, hydrogen peroxide and tetramethylhydrazine produced formaldehyde which was found to increase with either HRP or tetramethylhydrazine concentration. The cation radical, the dication, and the imine (the deprotonated dication) are proposed as intermediates in the mechanism of formaldehyde production.
doi_str_mv 10.1016/S0006-291X(82)80033-8
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subjects Armoracia lapathifolia
Carcinogens
E.S.R
Electron Spin Resonance Spectroscopy
Free Radicals
Horseradish Peroxidase - metabolism
Kinetics
Methylhydrazines
Oxidation-Reduction
peroxidase
Peroxidases - metabolism
tetramethylhydrazine
title An electron spin resonance study of a novel radical cation produced during the horseradish peroxidase-catalyzed oxidation of tetramethylhydrazine
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