Hypothesis paper
Role of metals in oxygen radical reactions

https://doi.org/10.1016/0748-5514(85)90025-XGet rights and content

Abstract

Partially-reduced forms of dioxygen or “oxy-radicals” (superoxide, O2HO2·; hydrogen peroxide H2O2; hydroxyl radical ·OH) and oxidants of comparable reactivity are implicated in an increasing number of physiological, toxicological, and pathological states. Transition metal catalysis is recognized as being integral to the generation and the reactions of these activated oxygen species. Factors such as pH and chelation govern the reactivity of the transition metals with dioxygen and “oxy-radicals” and therefore influence the apparent mechanisms by which oxidative damage to phospholipids, DNA, and other biomolecules is initiated. In biological systems the concentrations of redox-active transition metals capable of catalyzing these reactions appears to be relatively low. However, under certain conditions metal storage and transport proteins (ferritin, transferrin, ceruloplasmin, etc.) may furnish additional redox active metals.

References (297)

  • M.W. Sutherland et al.

    A reaction between superoxide free radical and lipid hydroperoxide in sodium linoleate micelles

    Arch. Biochem. Biophys.

    (1982)
  • M.J. Thomas et al.

    The role of the superoxide anion in the xanthine oxidase-induced autoxidation of linoleic acid

    Biochem. Biophys. Res. Commun.

    (1978)
  • K. Fukuzawa et al.

    Oxidation of α-tocopherol in micelles and liposomes and by the hydroxyl, perhydroxyl and superoxide free radicals

    Arch. Biochem. Biophys.

    (1983)
  • J. Butler et al.

    Reaction of iron-EDTA chelates with the superoxide radical

    Arch. Biochem. Biophys.

    (1982)
  • C. Bull et al.

    Iron-ethylenediaminetetraacetic acid (EDTA)-catalyzed superoxide dismutation revisited: An explanation of why the dismutase activity of Fe-EDTA cannot be detected in the cytochrome c-xanthine oxidase assay system

    Arch. Biochem. Biophys.

    (1982)
  • B. Halliwell

    The superoxide dismutase activity of iron complexes

    FEBS Lett.

    (1975)
  • B. Halliwell

    Superoxide-dependent formation of hydroxyl radicals in the presence of iron chelates: Is it a mechanism for OH radical in biological systems?

    FEBS Lett.

    (1978)
  • G.R. Buettner et al.

    The kinetics of the reaction of superoxide radical with Fe(III) complexes of EDTA, DETAPAC, and HEDTA

    FEBS Lett.

    (1983)
  • E. Graf et al.

    Iron-catalyzed hydroxyl radical formation: Stringent requirement for free iron coordination site

    J. Biol. Chem.

    (1984)
  • T. Ozawa et al.

    Spectroscopic studies on the reaction of superoxide ion with non-redox metalloporphyrins

    Inorg. Chim. Acta

    (1983)
  • M.J. Thomas et al.

    Studies on the reactivity of HO2·O2·̄ with unsaturated hydroperoxides in ethanolic solutions

    Arch. Biochem. Biophys.

    (1984)
  • C. Walling

    The nature of the primary oxidants in oxidations mediated by metal ions

  • S.D. Aust et al.

    The role of iron in enxymatic lipid peroxidation

  • K. Brawn et al.

    DNA strand scission by enzymatically generated oxygen radicals

    Arch. Biochem. Biophys.

    (1981)
  • A. Samuni et al.

    Unusual copper-induced sensitization of the biological damages due to superoxide radicals

    J. Biol. Chem.

    (1981)
  • R.A. Floyd

    Direct demonstration that ferrous ion complexes of di- and triphosphate nucleotides catalyze hydroxyl free radical formation from hydrogen peroxide

    Arch. Biochem. Biophys.

    (1983)
  • G. Cohen et al.

    The Fenton reaction between ferrous-diethylenetriaminepentaacetic acid and hydrogen peroxide

    FEBS Lett.

    (1982)
  • M. Tien et al.

    An investigation into the role of hydroxyl radical in xanthine oxidase-dependent lipid peroxidation

    Arch. Biochem. Biophys.

    (1982)
  • G. Just

    Kinetische untersuchung der autoxydation des in wasser gelösten ferrobicarbonats

    Chem. Ber.

    (1907)
  • M. Cher et al.

    The kinetics of the oxygenation of ferrous iron in phosphoric acid solution

    J. Am. Chem. Soc.

    (1954)
  • A.M. Posner

    The kinetics of autoxidation of ferrous ions in concentrated HCl solutions

    Trans. Faraday Soc.

    (1953)
  • J. Weiss

    The autoxidation of ferrous ions in aqueuos solution

    Experientia

    (1953)
  • W.M. Latimer

    Oxidative Potentials

    (1952)
  • J.A. Fee et al.

    Chemical and physical properties of superoxide

  • P. George

    The fitness of oxygen

  • A.B. Lamb et al.

    The electromotive activation of oxygen

    J. Am. Chem. Soc.

    (1931)
  • P. George

    The oxidation of ferrous perchlorate by molecular oxygen

    J. Chem. Soc.

    (1954)
  • J.R. Pound

    The oxidation of solutions of ferrous salts

    J. Phys. Chem.

    (1939)
  • D.-H. Chin et al.

    Detection and characterization of the long-postulated FeOOFe intermediate in the autoxidation of ferrous porphyrins

    J. Am. Chem. Soc.

    (1977)
  • G. Schwarzenbach et al.

    Komplexone XVIII. Die eisen(II)- und eisen(III)-komplexe des äthylenediamintetraessigsäure und ihr redoxgleichgewicht

    Helv. Chim. Acta

    (1951)
  • Y. Kurimura et al.

    Oxygen oxidation of ferrous ions induced by chelation

    Bull. Chem. Soc. Jap.

    (1968)
  • Y. Kurimura et al.

    The kinetics of the autoxidation of ferrous ions in aqueous tripolyphosphate solutions

    Bull. Chem. Soc. Jap.

    (1969)
  • P.E. Bumbry et al.

    Determination of nonheme iron, total iron and copper

  • K. Goto et al.

    The mechanism of oxygenation of ferrous ion in neutral solution

    Inorg. Chem.

    (1970)
  • P. Hemmerich

    Model studies on the binding of univalent and redox-active copper in proteins

  • A.D. Zuberbuhler

    Interactions of Cu(I) complexes with dioxygen

  • H.P. Misra et al.

    The role of superoxide anion in the autoxidation of epinephrine and a simple assay for superoxide dismutase

    J. Biol. Chem.

    (1972)
  • B. Halliwell

    Generation of hydrogen peroxide, superoxide and hydroxyl radicals during the oxidation of dihydroxyfumaric acid by peroxidase

    Biochem. J.

    (1977)
  • A.D. Gilmour et al.

    Kinetics of the reaction of molecular oxygen with iron(III)-cysteine complexes

    J. Chem. Soc.

    (1970)
  • Cited by (1058)

    • Good bacteria, oxidative stress and neurological disorders: Possible therapeutical considerations

      2022, Life Sciences
      Citation Excerpt :

      The H2O2 has been shown to be able to remove the inhibition of NF-κB in the cytosol and activate NF-κB, which leads to nuclear entry and stimulates the transcription of pro-inflammatory cytokines [61,62]. OH● is the most potent destructive mediator that reacts with lipids, proteins, nucleic acids and carbohydrates that is produced through interaction of H2O2 with O2● [63,64]. This free radical is able to damages DNA-protein cross-linking, stimulates lipid peroxidation and alters protein structure and function [65,66].

    View all citing articles on Scopus
    View full text