Oxygen radical chemistry of polyunsaturated fatty acids

doi:10.1016/0891-5849(89)90102-0

Free Radical Biology and Medicine

Volume 7, Issue 1, 1989, Pages 65-86

https://doi.org/10.1016/0891-5849(89)90102-0 Get rights and content

Abstract

Polyunsaturated fatty acids (PUFA) are readily susceptible to autoxidation. A chain oxidation of PUFA is initiated by hydrogen abstraction from allylic or biss-allylic positions leading to oxygenation and subsequent formation of peroxyl radicals. In media of low hydrogen-donating capacity the peroxyl radical is free to react further by competitive pathways resulting in cyclic peroxides, double bond isomerization and formation of dimers and oligomers. In the presence of good hydrogen donators, such as α-tocopherol or PUFA themselves, the peroxyl radical abstracts hydrogen to furnish PUFA hydroperoxides. Given the proper conditions or catalysts, the hydroperoxides are prone to further transformations by free radical routes. Homolytic cleavage of the hydroperoxy group can afford either a peroxyl radical or an alkoxyl radical. The products of peroxyl radicals are identical to those obtained during autoxidation of PUFA; that is, it makes no difference whether the peroxyl radical is generated in the process of autoxidation or from a performed hydroperoxide. Of particular interest is the intramolecular rearrangement of peroxyl radicals to furnish cyclic peroxides and prostaglandin-like bicyclo endoperoxides. Other principal peroxyl radical reactions are the β-scission of O₂, intermolecular addition and self-combination. Alkoxyl radicals of PUFA, contraty to popular belief, do not significantly abstract hydrogens, but rather are channeled into epoxide formation through intramolecular rearrangement. Other significant reactions of PUFA alkoxyl radicals are β-scission of the fatty chain and possibly the formation of ether-linked dimers and oligomers. Although homolytic reactions of PUFA hydroperoxides have received the most attention, hydroperoxides are also susceptible to heterolytic transformations, such as nuleophilic displacement and acid-catalyzed rearrangement.

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^∗: The mention of trade names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.

^∗∗: Harold W. Gardner, a native of Carlisle, Pennsylvania, received BS and PhD degrees in biochemistry at Pennsylvania State University. After postdoctoral work at University of California at Los Angeles and research at the Pineapple Research Institute in Honolulu, he moved to the Northern Regional Research Center, Peoria, Illinois, where he currently is engaged in plant biochemical research. He has been the author or coauthor of over 50 publications, principally in the chemistry and biochemistry of lipid hydroperoxides. Recent research has included the causes of fungal resistance to potato phytoalexins, plant ethylene biosynthesis, the study of maize amyloplast membranes, action mechanism of soy lipoxygenase-1, characterization of soy hydroperoxide lyase and the physiological effects of the “linoleic acid/linolenic acid cascade” in plants. He is also a conservationist specializing in the restoration and propagation of native prairie plants.

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Review articleOxygen radical chemistry of polyunsaturated fatty acids

Abstract

Biochim. Biophys. Acta

J. Biol. Chem.

Anal. Biochem.

Biochim. Biophys. Acta

Biochim. Biophys. Acta

J. Free Radicals Biol. Med.

Chem. Phys. Lipids.

Biochim. Biophys. Acta

Tetrahedron

Tetrahedron Lett.

Chem. Phys. Lipids

J. Chromatog.

Phytochemistry

Arch. Biochem. Biophys.

Chem. Phys. Lipids

Biochim. Biophys. Acta

Chem. Phys. Lipids

Biochim. Biophys. Acta

Prog. Lipid Res.

Arch. Biochem. Biophys.

J. Biol. Chem.

Biochim. Biophys. Acta

Biochim. Biophys. Acta

The course of autoxidation reactions in polyisoprenes and allied compounds. Part VII. Rearrangement of double bonds during autoxidation

J. Chem. Soc.

Mechanisms for the autoxidation of polyunsaturated lipids

Acc. Chem. Res.

Chemistry of free radical and singlet oxidation of lipids

Prog. Lipid Res.

The kinetics of the autoxidation of polyunsaturated fatty acids

Lipids

Thermal isomerisation of methyl linoleate hydroperoxides. Evidence of molecular oxygen as a leaving group in a radical rearrangement

J. Chem. Soc. Chem. Commun.

A hydroperoxyepidioxide from the autoxidation of a hydroperoxide of methyl linolase

J. Chem. Soc. Chem. Commun.

Autoxidation of polyunsaturated lipids. Factors controlling the stereochemistry of product hydroperoxides

J. Am. Chem. Soc.

Unified mechanism for polyunsaturated fatty acid autoxidation. Competition of peroxyl radical hydrogen atom abstraction. β-scission, and cyclization

J. Am. Chem. Soc.

Autoxidation of polyunsaturated fatty acids, an expanded mechanistic study

J. Am. Chem. Soc.

Autoxidation of methyl linolenate and methyl linoleate: the effect of α-tocopherol

J. Sci. Food Agric.

Selective formation of dihydroperoxides in the α-tocopherol inhibited autoxidation of methyl linolenate

J. Chem. Soc. Commun.

High pressure liquid chromatography of autoxidized lipids: II. Hydroperoxy-cyclic peroxides and other secondary products from methyl linolenate

Lipids

Stereochemistry of olefin and fatty acid oxidation. Part 3. The allylic hydroperoxides from the autoxidation of methyl oleate

J. Chem. Soc. Perkin Trans.

Allylic hydroperoxide rearrangement: β-scission or concerted pathway?

J. Org. Chem.

Detection of monohydroperoxides with unconjugated diene systems as minor products of the autoxidation of methyl linoleate

Z. Lebensm. Unters. Forsch.

Autoxidation of phenyl linoleat and phenyl oleate: HPLC analysis of the major and minor monohydroperoxides as phenyl stearates

Lipids

Lipids

Preparation and purification of lipid hydroperoxides from arachidonic and γ-linolenic acids

Lipids

Lipoxygenase from Zea mays: 9-D-Hydroperoxy-trans-10,cis-12-octadecadienoic acid from linoleic acid

Lipids

Lipoxygenase from potato tubers. Partial purification and properties of an enzyme that specifically oxygenates the 9-position of linoleic acid

Biochem. J.

A simple method for the preparation of pure 9-D-hydroperoxide of linoleic acid and methyl linoleate based on the positional specificity of lipoxygenase in tomato fruit

Lipids

Optically active long-chain compounds and their absolute configurations

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

Biochem. J.

Catalytic and stoichiometric process involving oxidation-reduction reactions

The course of autoxidation reactions in polyisoprenes and allied compounds. Part IX. The primary thermal oxidation product of ethyl linoleate

J. Chem. Soc.

Deuterium-isotope effects in the autoxidation of aralkyl hydrocarbons. Mechanisms of the interaction of peroxy radicals

J. Am. Chem. Soc.

Review article
Oxygen radical chemistry of polyunsaturated fatty acids