Lipid oxidation: Mechanisms, products and biological significance

This paper reviews our studies of fatty acid hydroperoxides, their secondary products and mechanisms for their formation in the context of some of their possible biological consequences. The uneven distribution of isomeric hydroperoxides in oxidized linolenate and photosensitized oxidized linoleate is related to the formation of hydroperoxy cyclic peroxides. Interest in the hydroperoxy mono-and bi-cycloendoperoxides from oxidized linolenate stems from their structural relationship to the prostaglandins. However, the biological activity of hydroperoxy cyclic peroxides formed by autoxidation has not yet been reported. Thermal decomposition studies of secondary lipid oxidation products show they are important precursors of volatile compounds. An acid-acetalation decomposition procedure establishes that 5-membered hydroperoxy cyclic peroxides and 1,3-dihydroperoxides are important precursors of malonaldehyde. This approach provides a more specific test than the thiobarbituric acid (TBA) color reaction to evaluate lipid oxidation products as sources of malonaldehyde and its biological effects due to crosslinking. A better understanding is needed of the biological effects of a multitude of lipid oxidation decomposition products other than malonaldehyde.

[1]  W. Pryor.  THE FORMATION OF FREE RADICALS AND THE CONSEQUENCES OF THEIR REACTIONS IN VIVO , 1978, Photochemistry and photobiology.

[2]  H. Rawls,et al.  SINGLET OXYGEN: A POSSTBLE SOURCE OF THE ORIGINAL HYDROPEROXIDES IN FATTY ACIDS , 1970 .

[3]  D. Nugteren,et al.  Non-enzymic conversion of all-cis 8 11 14-eicosatriencoic acid into prostaglandin E1. , 2010 .

[4]  A. Bender,et al.  Pharmacological control of aging. , 1970, Experimental gerontology.

[5]  R. Bhatnagar.  Molecular Basis of Environmental Toxicity , 1980 .

[6]  E. D. Mihelich,et al.  Isolation and characterization of bicycloendoperoxides derived from methyl linolenate , 1981 .

[7]  M. Karel,et al.  Interaction of peroxidizing methyl linoleate with some proteins and amino acids. , 1975, Journal of agricultural and food chemistry.

[8]  B. Halliwell.  Tocopherol, Oxygen and Biomembranes : Edited by C. de Duve and O. Hayaishi Elsevier/North-Holland Biomedical Press; Amsterdam, New York, 1978 xiv + 374 pages. Dfl 107.00; $46.75 , 1978 .

[9]  N. Porter,et al.  Serial Cyclization of an Arachidonic Acid Hydroperoxide , 1982 .

[10]  B. Weedon,et al.  Stereochemistry of olefin and fatty acid oxidation. Part 2. Photosensitised oxidation of hexene and hepta-2,5-diene isomers , 1982 .

[11]  H. Bartsch,et al.  On the metabolic activation of the carcinogen N-hydroxy-N-2-acetylaminofluorene. 3. Oxidation with horseradish peroxidase to yield 2-nitrosofluorene and N-acetoxy-N-2-acetylaminofluorene. , 1971, Biochimica et biophysica acta.

[12]  M. Funk,et al.  The formation of cyclic peroxides from unsaturated hydroperoxides: Models for prostaglandin biosynthesis. , 1976, Journal of the American Chemical Society.

[13]  J. Johnson,et al.  CHAPTER 4 – Lipofuscin: Fine-Structural and Biochemical Studies , 1977 .

[14]  M. Funk,et al.  Letter: Peroxy radical cyclization as a model for prostaglandin biosynthesis. , 1975, The Journal of organic chemistry.

[15]  E. L. Powers,et al.  Oxygen and oxy-radicals in chemistry and biology , 1981 .

[16]  E. Selke,et al.  Autoxidation of Methyl Linolenate. Isolation and Characterization of Hydroperoxides2 , 1961 .

[17]  H. Gardner.  Lipid hydroperoxide reactivity with proteins and amino acids: a review , 1979 .

[18]  D. Forss.  Odor and flavor compounds from lipids. , 1972, Progress in the chemistry of fats and other lipids.

[19]  W. Caspary,et al.  Enzymic formation of 6-oxobenzo[a]pyrene radical in rat liver homogenates from carcinogenic benzo[a]pyrene , 1975 .

[20]  R. Shamberger,et al.  Malonaldehyde content of food. , 1977, The Journal of nutrition.

[21]  E. Frankel,et al.  Formation of malonaldehyde from lipid oxidation products , 1983 .

[22]  S. Patton,et al.  2-Thiobarbituric Acid as a Reagent for Detecting Milk Fat Oxidation , 1951 .

[23]  R. Floyd,et al.  Lipid hydroperoxide activation of N-hydroxy-N-acetylaminofluorene via a free radical route. , 1976, Cancer research.

[24]  Bruce A. Weber,et al.  Autoxidation of polyunsaturated lipids. Factors controlling the stereochemistry of product hydroperoxides , 1980 .

[25]  M. Uchiyama,et al.  Determination of malonaldehyde precursor in tissues by thiobarbituric acid test. , 1978, Analytical biochemistry.

[26]  J. Koster,et al.  Lipid peroxidation of rat liver microsomes. , 1980, Biochimica et biophysica acta.

[27]  B. Samuelsson.  Chapter IV – Structures, Biosynthesis, and Metabolism of Prostaglandins , 1970 .

[28]  E. D. Mihelich.  Structure and stereochemistry of novel endoperoxides isolated from the sensitized photooxidation of methyl linoleate. Implications for prostaglandin biosynthesis , 1980 .

[29]  P. Begemann,et al.  Structure of four methyl linolenate diperoxides , 1968 .

[30]  W. Caspary,et al.  Autoxidation of 6-hydroxybenzo(a)pyrene and 6-oxobenzo(a)pyrene radical, reactive metabolites of benzo(a)pyrene , 1975 .

[31]  A. Francke,et al.  Cyclic peroxides from a soya lipoxygenase-catalysed oxygenation of methyl linolenate. , 1978, Biochimica et biophysica acta.

[32]  E. Frankel.  Volatile lipid oxidation products. , 1983, Progress in lipid research.

[33]  S. Matsushita.  Specific interactions of linoleic acid hydroperoxides and their secondary degraded products with enzyme proteins. , 1975, Journal of agricultural and food chemistry.

[34]  C. E. West,et al.  Minireview possible roles of dietary fats in carcinogenesis , 1976 .

[35]  H. Bartsch,et al.  On the metabolic activation of N-hydroxy-N-2-acetylamino-fluorene. II. Simultaneous formation of 2-nitrosofluorene and N-acetoxy-N-2-acetylaminofluorene from N-hydroxy-N-2-acetylaminofluorene via a free radical intermediate. , 1971, Biochimica et biophysica acta.

[36]  D. T. Coxon,et al.  Formation, isolation and structure determination of methyl linolenate diperoxides , 1981 .

[37]  R. Floyd.  Free radicals and cancer , 1982 .

[38]  N. Porter,et al.  Cyclic peroxides and the thiobarbituric assay. , 1976, Biochimica et biophysica acta.

[39]  M. Sporn,et al.  13-cis-retinoic acid: inhibition of bladder carcinogenesis in the rat. , 1977, Science.

[40]  Bruce A. Weber,et al.  Unified mechanism for polyunsaturated fatty acid autoxidation. Competition of peroxy radical hydrogen atom abstraction, .beta.-scission, and cyclization , 1981 .

[41]  Robert B. Wilson,et al.  Lipid Peroxidation and atherosclerosis , 1976 .

[42]  W. Pryor.  Free Radicals in Biology , 1976 .

[43]  B. Goldstein,et al.  Mutagenicity of malonaldehyde, a decomposition product of peroxidized polyunsaturated fatty acids. , 1976, Science.

[44]  A. Tappel,et al.  Inactivation of ribonuclease and other enzymes by peroxidizing lipids and by malonaldehyde. , 1969, Biochemistry.

[45]  C. Foote,et al.  Activated oxygen species and oxidation of food constituents. , 1978, CRC critical reviews in food science and nutrition.