Preferences help
enabled [disable] Abstract
Number of results
2000 | 47 | 4 | 923-930
Article title

Lipid radicals: Properties and detection by spin trapping.

Title variants
Languages of publication
Unsaturated lipids are rapidly oxidized to toxic products such as lipid hydroperoxides, especially when transition metals such as iron or copper are present. In a Fenton-type reaction Fe2+ converts lipid hydroperoxides to the very short-lived lipid alkoxyl radicals. The reaction was started upon the addition of Fe2+ to an aqueous linoleic acid hydroperoxide (LOOH) emulsion and the spin trap in the absence of oxygen. Even when high concentrations of spin traps were added to the incubation mixture, only secondary radical adducts were detected, probably due to the rapid rearrangement of the primary alkoxyl radicals. With the commercially available nitroso spin trap MNP we observed a slightly immobilized ESR spectrum with only one hydrogen splitting, indicating the trapping of a methinyl fragment of a lipid radical. With DMPO or 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO) adducts were detected with carbon-centered lipid radical, with acyl radical, and with the hydroxyl radical. We also synthesized lipophilic derivatives of the spin trap DEPMPO in order to detect lipid radical species generated in the lipid phase. With all spin traps studied a lipid-derived carbon-centered radical was obtained in the anaerobic incubation system Fe2+/LOOH indicating the trapping of a lipid radical, possibly generated as a secondary reaction product of the primary lipid alkoxyl radical formed. Under aerobic conditions an SOD-insensitive oxygen-centered radical adduct was formed with DEPMPO and its lipophilic derivatives. The observed ESR parameters were similar to those of alkoxyl radical adducts, which were independently synthesized in model experiments using Fe3+-catalyzed nucleophilic addition of methanol or t-butanol to the respective spin trap.

Physical description
  • Institute of Pharmacology and Toxicology, Veterinary University of Vienna, A-1210 Vienna, Austria
  • Institute of Pharmacology and Toxicology, Veterinary University of Vienna, A-1210 Vienna, Austria
  • Institute of Pharmacology and Toxicology, Veterinary University of Vienna, A-1210 Vienna, Austria
  • 1. Marnett, L.J. (1987) Peroxyl free radicals: Potential mediators of tumor initiation and promotion. Carcinogenesis 8, 1365-1373.
  • 2. DeGroot, J.J.M.C., Garssen, G.J., Vliegenhardt, J.F.G. & Boldingh, J. (1973) The detection of linoleic acid radicals in the anaerobic reaction of lipoxygenase. Biochim. Biophys. Acta 326, 279-284.
  • 3. Garlick, P.B., Davies, M.J., Hearse, D.J. & Slater, T.F. (1987) Direct detection of free radicals in the reperfused rat heart using electron spin resonance spectroscopy. Circ. Res. 61, 757-760.
  • 4. Janzen, E.G., Kotake, Y. & Hinton, R.D. (1992) Stabilities of hydroxyl radical spin adducts of PBN-type spin traps. Free Radic. Biol. Med. 12, 169-173.
  • 5. Buettner, G.R. & Oberley, L.W. (1978) 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. 83, 69-74.
  • 6. Fréjaville, C., Karoui, H., Tuccio, B., Le Moigne, F., Culcasi, M., Pietri, S., Lauricella, R. & Tordo, P. (1995) 5-(Diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide: A new efficient phosphorylated nitrone for the in vitro and in vivo spin trapping of oxygen-centered radicals. J. Med. Chem. 38, 258-265.
  • 7. Sawa, T., Akaike, T., Kida, K., Fukushima, Y., Takagi, K. & Maeda, H. (1998) Lipid peroxyl radicals from oxidized oils and heme-iron: Implication of a high-fat diet in colon carcinogenesis. Cancer Epidemiol. Biomarkers Prev. 7, 1007-1012.
  • 8. Bartsch, H., Nair, J. & Owen, R.W. (1999) Dietary polyunsaturated fatty acids and cancers of the breast and colorectum: Emerging evidence for their role as risk modifiers. Carcinogenesis 20, 2209-2218.
  • 9. Stolze, K., Udilova, N. & Nohl, H. (2000) Spin trapping of lipid radicals with DEPMPO-derived spin traps. Detection of superoxide, alkyl and alkoxyl radicals in aqueous and lipid phase. Free Radic. Biol. Med. 29, 1005-1014.
  • 10. Barbati, S., Clément, J. L., Olive, G., Roubaud, V., Tuccio, B. & Tordo, P. (1997) 31P-Labeled cyclic nitrones: A new class of spin traps for free radicals in biological milieu; in Free Radicals in Biology and Environment (Minisci, F., ed.) pp. 39-47, Kluwer Academic Publishers, Dordrecht.
  • 11. O'Brien, P.J. (1969) 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. 47, 485-492.
  • 12. Rota, C., Barr, D.P., Martin, M. V., Guengerich, F.P., Tomasi, A. & Mason, R.P. (1997) Detection of free radicals produced from the reaction of cytochrome P-450 with linoleic acid hydroperoxide. Biochem. J. 328, 565-571.
  • 13. Dikalov, S.I. & Mason, R.P. (1999) Reassignment of organic peroxyl radical adducts. Free Radic. Biol. Med. 27, 864-872.
  • 14. Iwahashi, H. (1991) Radical adducts of nitrosobenzene and 2-methyl-2-nitrosopropane with 12,13-epoxylinoleic acid radical, 12,13- epoxylinoleic acid radical and 14,15-epoxyarachidonic acid radical. Biochem. J. 276, 447-453.
  • 15. Chamulitrat, W. & Mason, R.P. (1990) Alkyl free radicals from the β-scission of fatty acid alkoxyl radicals as detected by spin trapping in a lipoxygenase system. Arch. Biochem. Biophys. 282, 65-69.
  • 16. Reeder, B.J. & Wilson, M.T. (1998) Mechanism of reaction of myoglobin with the lipid hydroperoxide hydroperoxyoctadecadienoic acid. Biochem. J. 330, 1317-1323.
  • 17. van der Zee, J., Barr, D.P. & Mason, R.P. (1996) ESR spin trapping investigation of radical formation from the reaction between hematin and tert-butyl hydroperoxide. Free Radic. Biol. Med. 20, 199-206.
  • 18. Akaike, T., Sato, K., Ijiri, S., Miyamoto, Y., Kohno, M., Ando, M. & Maeda, H. (1992) Bactericidal activity of alkyl peroxyl radicals generated by heme-iron-catalyzed decomposition of organic peroxides. Arch. Biochem. Biophys. 294, 55-63.
  • 19. Kalyanaraman, B., Mottley, C. & Mason, R.P. (1983) A direct ESR and spin-trapping investigation of peroxyl free radical formation by hematin/hydroperoxide systems. J. Biol. Chem. 258, 3855-3858.
  • 20. Chamulitrat, W., Takahashi, N. & Mason, R.P. (1989) Peroxyl, alkoxyl, and carbon-centered radical formation from organic hydroperoxides by chloroperoxidase. J. Biol. Chem. 264, 7889-7899.
  • 21. Davies, M.J. (1988) Detection of peroxyl and alkoxyl radicals produced by reaction of hydroperoxides with heme-proteins by ESR spectrocopy. Biochim. Biophys. Acta 964, 28-35.
  • 22. Davies, M.J. (1989) Detection of peroxyl and alkoxyl radicals produced by reaction of hydroperoxides with rat liver microsomal fractions. Biochem. J. 257, 603-606.
Document Type
Publication order reference
YADDA identifier
JavaScript is turned off in your web browser. Turn it on to take full advantage of this site, then refresh the page.