Formation of superoxide anion during ferrous ion-induced decomposition of linoleic acid hydroperoxide under aerobic conditions

J Biochem. 2003 Dec;134(6):903-9. doi: 10.1093/jb/mvg217.

Abstract

We studied the mechanism of formation of oxygen radicals during ferrous ion-induced decomposition of linoleic acid hydroperoxide using the spin trapping and chemiluminescence methods. The formation of the superoxide anion (O2*-) was verified in the present study. The hydroxyl radical is also generated through Fenton type decomposition of hydrogen peroxide produced on disproportionation of O2*-. A carbon-centered radical was detected using 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO) as a spin trap. Alkoxyl radical formation is essential for the conversion of linoleic acid hydroperoxide into the peroxyl radical by ferrous ion. It is likely that the alkoxyl radical [R1CH(O*)R2] is converted into the hydroxylcarbon radical [R1C*(OH)R2] in water, and that this carbon radical reacts with oxygen to give the alpha-hydroxyperoxyl radical [R1R2C(OH)OO*], which decomposes into the carbocation [R1C+(OH)R2] and O2*-.

MeSH terms

  • Aerobiosis
  • Argon / chemistry
  • Catalysis
  • Cyclic N-Oxides / chemistry
  • Electron Spin Resonance Spectroscopy
  • Ferrous Compounds / chemistry*
  • Free Radicals / chemistry
  • Linoleic Acids / chemistry
  • Linoleic Acids / metabolism*
  • Lipid Peroxides / chemistry
  • Lipid Peroxides / metabolism*
  • Luminescent Measurements
  • Spin Labels
  • Spin Trapping
  • Superoxides / chemistry*
  • Superoxides / metabolism*

Substances

  • Cyclic N-Oxides
  • Ferrous Compounds
  • Free Radicals
  • Linoleic Acids
  • Lipid Peroxides
  • Spin Labels
  • Superoxides
  • linoleic acid hydroperoxide
  • Argon
  • 5,5-dimethyl-1-pyrroline-1-oxide