Transition metals as catalysts of “autoxidation” reactions

Dennis M Miller; Garry R Buettner; Steven D Aust

doi:10.1016/0891-5849(90)90148-C

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Transition metals as catalysts of “autoxidation” reactions

Journal article

Peer reviewed

Transition metals as catalysts of “autoxidation” reactions

Dennis M Miller, Garry R Buettner and Steven D Aust

Free Radical Biology and Medicine, Vol.8(1), pp.95-108

1990

DOI: 10.1016/0891-5849(90)90148-C

PMID: 2182396

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Abstract

Superoxide (O 2 − ̇ , hydrogen peroxide (H 2O 2), and hydroxyl radical (·OH) produced from the “autoxidation” of biomolecules, such as ascorbate, catecholamines, or thiols, have been implicated in numerous toxicities. However, the direct reaction of dioxygen with the vast majority of biomolecules, including those listed above, is spin forbidden, a condition which imposes a severe kinetic limitation on this reaction pathway. Therefore, an alternate mechanism must be invoked to explain the “autoxidations” reactions frequently reported. Transition metals are efficient catalysts of redox reactions and their reactons with dioxygen are not spin restricted. Therefore it is likely that the “autoxidation” observed for many biomolecules is, in fact, metal catalyzed. In this paper we discuss: 1) the quantum mechanic, thermodynamic, and kinetic aspects of the reaction of dioxygen with biomolecules; 2) the involvement of transition metals in biomolecule oxidation; and 3) the biological implications of metal catalyzed oxidations. We hypothesize that true autoxidation of biomolecules does not occcur in biological systems, instead the “autoxidation” of biomolecules is the result of transition metals bound by the biomolecules.

Iron

Autoxidation

Free radicals

Chelation

Superoxide

Hydroxyl radical

Peroxidation

Details

Title: Subtitle: Transition metals as catalysts of “autoxidation” reactions
Creators: Dennis M Miller - Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, U.S.A
Garry R Buettner - The University of Iowa, College of Medicine, ESR Facility, HBRF 58, Iowa City, IA 52242, U.S.A
Steven D Aust - Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, U.S.A
Resource Type: Journal article
Publication Details: Free Radical Biology and Medicine, Vol.8(1), pp.95-108
DOI: 10.1016/0891-5849(90)90148-C
PMID: 2182396
NLM abbreviation: Free Radic Biol Med
ISSN: 0891-5849
eISSN: 1873-4596
Publisher: Elsevier Inc
Language: English
Date published: 1990
Academic Unit: Radiation Oncology
Record Identifier: 9984046819802771

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