• We are sorry, but NCBI web applications do not support your browser and may not function properly. More information
Logo of biochemjBJ Latest papers and much more!
Biochem J. Jul 1, 1987; 245(1): 167–173.
PMCID: PMC1148096

Studies on the metal-ion and lipoxygenase-catalysed breakdown of hydroperoxides using electron-spin-resonance spectroscopy.

Abstract

The breakdown of cumene hydroperoxide and peroxidized fatty acids by iron is shown, by use of the spin trap 5,5-dimethyl-l-pyrroline-N-oxide, to be sensitive to (a) the oxidation state of the metal and (b) the nature of the chelating ligands. The initial step in the Fe2+-catalysed breakdown is the production of an alkoxyl radical by one-electron reduction, and this type of radical has been successfully trapped from each substrate. Subsequent reactions of this alkoxyl species produce both carbon-centred and peroxyl radicals, depending on the concentrations of the reagents present. The use of the same spin trap in microsomal systems undergoing either NADPH-supported or Fe2+-induced peroxidation led to the detection of low concentrations of radical adducts, among which are signals that are believed to be due to lipid alkoxyl radicals. Reaction of polyunsaturated fatty acid hydroperoxides with both Fe2+ and lipoxygenase under anaerobic conditions gives rise to signals not only from the alkoxy-radical adduct, but also from a further species which is tentatively identified as being due to an acyl [RC(O).]-radical adduct; chemical studies lend support to this assignment.

Full text

Full text is available as a scanned copy of the original print version. Get a printable copy (PDF file) of the complete article (1.3M), or click on a page image below to browse page by page. Links to PubMed are also available for Selected References.

Selected References

These references are in PubMed. This may not be the complete list of references from this article.
  • Albano E, Lott KA, Slater TF, Stier A, Symons MC, Tomasi A. Spin-trapping studies on the free-radical products formed by metabolic activation of carbon tetrachloride in rat liver microsomal fractions isolated hepatocytes and in vivo in the rat. Biochem J. 1982 May 15;204(2):593–603. [PMC free article] [PubMed]
  • Buettner GR, Oberley LW. Considerations in the spin trapping of superoxide and hydroxyl radical in aqueous systems using 5,5-dimethyl-1-pyrroline-1-oxide. Biochem Biophys Res Commun. 1978 Jul 14;83(1):69–74. [PubMed]
  • Butler J, Halliwell B. Reaction of iron-EDTA chelates with the superoxide radical. Arch Biochem Biophys. 1982 Oct 1;218(1):174–178. [PubMed]
  • Davies MJ, Slater TF. Studies on the photolytic breakdown of hydroperoxides and peroxidized fatty acids by using electron spin resonance spectroscopy. Spin trapping of alkoxyl and peroxyl radicals in organic solvents. Biochem J. 1986 Dec 15;240(3):789–795. [PMC free article] [PubMed]
  • Dix TA, Marnett LJ. Conversion of linoleic acid hydroperoxide to hydroxy, keto, epoxyhydroxy, and trihydroxy fatty acids by hematin. J Biol Chem. 1985 May 10;260(9):5351–5357. [PubMed]
  • Finkelstein E, Rosen GM, Rauckman EJ, Paxton J. Spin trapping of superoxide. Mol Pharmacol. 1979 Sep;16(2):676–685. [PubMed]
  • Gardner HW. Decomposition of linoleic acid hydroperoxides. Enzymic reactions compared with nonenzymic. J Agric Food Chem. 1975 Mar-Apr;23(2):129–136. [PubMed]
  • Gardner HW, Jursinic PA. Degradation of linoleic acid hydroperoxides by a cysteine . FeCl3 catalyst as a model for similar biochemical reactions. I. Study of oxygen requirement, catalyst and effect of pH. Biochim Biophys Acta. 1981 Jul 24;665(1):100–112. [PubMed]
  • Gutteridge JM, Richmond R, Halliwell B. Inhibition of the iron-catalysed formation of hydroxyl radicals from superoxide and of lipid peroxidation by desferrioxamine. Biochem J. 1979 Nov 15;184(2):469–472. [PMC free article] [PubMed]
  • Halliwell B, Gutteridge JM. Oxygen toxicity, oxygen radicals, transition metals and disease. Biochem J. 1984 Apr 1;219(1):1–14. [PMC free article] [PubMed]
  • Hawco FJ, O'Brien PJ. Singlet oxygen formation during hemoprotein catalyzed lipid peroxide decomposition. Biochem Biophys Res Commun. 1976 May 23;76(2):354–361. [PubMed]
  • Hrycay EG, O'Brien PJ. Cytochrome P-450 as a microsomal peroxidase utilizing a lipid peroxide substrate. Arch Biochem Biophys. 1971 Nov;147(1):14–27. [PubMed]
  • Kalyanaraman B, Mottley C, Mason RP. A direct electron spin resonance and spin-trapping investigation of peroxyl free radical formation by hematin/hydroperoxide systems. J Biol Chem. 1983 Mar 25;258(6):3855–3858. [PubMed]
  • Marnett LJ. Polycyclic aromatic hydrocarbon oxidation during prostaglandin biosynthesis. Life Sci. 1981 Aug 10;29(6):531–546. [PubMed]
  • O'Brien PJ. Intracellular mechanisms for the decomposition of a lipid peroxide. I. Decomposition of a lipid peroxide by metal ions, heme compounds, and nucleophiles. Can J Biochem. 1969 May;47(5):485–492. [PubMed]
  • Porter NA. Chemistry of lipid peroxidation. Methods Enzymol. 1984;105:273–282. [PubMed]
  • Pryor WA. Free radical reactions and their importance in biochemical systems. Fed Proc. 1973 Aug;32(8):1862–1869. [PubMed]
  • Schaich KM. Free radical initiation in proteins and amino acids by ionizing and ultraviolet radiations and lipid oxidation--part III: free radical transfer from oxidizing lipids. Crit Rev Food Sci Nutr. 1980;13(3):189–244. [PubMed]
  • Slater TF, Sawyer BC. The stimulatory effects of carbon tetrachloride and other halogenoalkanes on peroxidative reactions in rat liver fractions in vitro. General features of the systems used. Biochem J. 1971 Aug;123(5):805–814. [PMC free article] [PubMed]
  • Svingen BA, Buege JA, O'Neal FO, Aust SD. The mechanism of NADPH-dependent lipid peroxidation. The propagation of lipid peroxidation. J Biol Chem. 1979 Jul 10;254(13):5892–5899. [PubMed]
  • TAPPEL AL, BOYER PD, LUNDBERG WO. The reaction mechanism of soy bean lipoxidase. J Biol Chem. 1952 Nov;199(1):267–281. [PubMed]
  • Wills ED. Mechanisms of lipid peroxide formation in animal tissues. Biochem J. 1966 Jun;99(3):667–676. [PMC free article] [PubMed]

Articles from Biochemical Journal are provided here courtesy of The Biochemical Society

Formats:

Related citations in PubMed

See reviews...See all...

Cited by other articles in PMC

See all...

Links

  • Compound
    Compound
    PubChem Compound links
  • MedGen
    MedGen
    Related information in MedGen
  • PubMed
    PubMed
    PubMed citations for these articles
  • Substance
    Substance
    PubChem Substance links

Recent Activity

Your browsing activity is empty.

Activity recording is turned off.

Turn recording back on

See more...