Abstract
Fat autoxidation produces flavor deterioration in lipid-containing foods and may decrease assurance of their nutritional quality and safety. Although the classical problems of oxidative deterioration in foods have considerable economic importance, they are now overshadowed by the biological problems of lipid peroxidation that cause damage to membranes, enzymes, vitamins, proteins and vital cell functions. There is now evidence that singlet oxygen plays a role in initiating autoxidation in unsaturated fats.1–4 Singlet oxygen, superoxide and other species of activated oxygen have also been implicated in many biological oxidation processes,5–9 in aging,8,10 as well as in environmental pollution.11–13 For these reasons, there is renewed interest in the problems of fat autoxidation, and oxidation chemistry has become an intensively active area of research.14–19 This review discusses different analytical tools applied in our laboratory to the study of autoxidation. The last section of this review deals with some mechanistic implications of our results.
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References
H. R. Rawls and P. J. Van Santen, A possible role for singlet oxygen in the initiation of fatty acid autoxidation, J. Am. Oil Chem. Soc. 47: 121 (1970).
H. R. Rawls and P. J. Van Santen, A possible source of the original hydroperoxides in fatty acids, Ann. N.Y. Acad. Sci. 171: 135 (1970).
A. H. Clements, R. H. Van den Engh, D. J. Frost, K. Hoogenhout, and J. R. Nooi, Participation of singlet oxygen in photosensitized oxidation of 1,4-dienoic systems and photo-oxidation of soybean oil, J. Am. Oil Chem. Soc. 50: 325 (1973).
D. J. Carlsson, T. Suprunchuk, and D. M. Wiles, Photooxidation of unsaturated oils: Effect of singlet oxygen quenchers, J. Am. Oil Chem. Soc. 53: 656 (1976).
M. L. Kaplan, “Singlet” oxygen, Chem. Tech. 621 (1971).
C. S. Foote, Photosensitized oxidation and singlet oxygen: consequences in biological soybeans, in “Free Radicals in Biology,” W. A. Pryor, ed., Vol. II, Academic Press, New York (1976).
I. Fridovich, Oxygen radicals, hydrogen peroxide and oxygen toxicity, in “Free Radicals in Biology,” W. A. Pryor, ed., Vol. I, Academic Press, New York (1976).
J. Bland, Biochemical effects of excited state molecular oxygen, J. Chem. Ed. 53:274 (1976).
N. I. Krinsky, Singlet oxygen in biological systems, Trends in Biochem. Sci. 2:35 (1977).
L. Packer and J. Walton, Antioxidants vs. aging, Chem. Tech. 276 (1977).
P. A. Leighton, “Photochemistry of Air Pollution,” Academic Press, New York (1961).
R. H. Kummler, M. H. Bortner, and T. Baurer, Hartley photolysis of ozone as a source of singlet oxygen in polluted atmosphere, Environ. Sci. Technol. 3:248 (1969).
J. N. Pitts, Jr., A. V. Khan, E. B. Smith, and R. P. Wayne, Singlet oxygen in the environmental sciences: singlet molecular oxygen and photochemical air pollution, Environ. Sci. Technol. 3:241 (1969).
W. A. Pryor, The role of free radical reactions in biological systems, in “Free Radicals in Biology,” W. A. Pryor, ed., Vol. I, Academic Press, New York (1976).
E. Lee-Ruff, The organic chemistry of superoxide, Chem. Soc. Rev. 6:195 (1977).
M. B. Korycka-Dahl and T. Richardson, Activated oxygen species and oxidation of food constituents. CRC Crit. Rev. Food Sci. Nutr. 11:209 (1978).
A. Singh and A. Petkan, eds., Singlet oxygen and related species in chemistry and biology, Photochem. Photobiol. 28:429934 (1978).
B. Ranby and J. F. Rabek, eds., “Singlet oxygen reactions with organic compounds and polymers,” John Wiley and Sons, New York (1978).
H. H. Wasserman and R. W. Murray, eds., “Singlet Oxygen,” Academic Press, New York (1979).
E. N. Frankel, C. D. Evans, D. G. McConnell, and E. P. Jones, Analyses of lipids and oxidation products by Partition chromatography. Fatty acid hydroperoxides, J. Am. Oil Chem. Soc. 38: 134 (1961).
E. Selke, E. N. Frankel, and W. E. Neff, Thermal decomposition of methyl oleate hydroperoxides and identification of volatile components by gas chromatography-mass spectrometry, Lipids 13: 511 (1978).
P. Budowski, I. Bartov, Y. Dror, and E. N. Frankel, Lipid oxidation products and chick nutritional encephalopathy, Lipids 14: 768 (1979).
E. N. Frankel, Hydroperoxides, in “Symposium on Foods: Lipids and Their Oxidation,” H. W. Schultz, E. A. Day, and R. O. Sinnhuber, eds., Avi Publishing Co., Westport (1962).
E. N. Frankel, J. Nowakowska, and C. D. Evans, Formation of methyl azelaaldehydate on autoxidation of lipids, J. Am. Oil Chem. Soc. 38: 161 (1961).
E. N. Frankel, C. D. Evans, D. G. McConnell, E. Selke, and H. J. Dutton, Autoxidation of methyl linolenate. Isolation and characterization of hydroperoxides, J. Org. Chem. 26:4663 (1961).
J. Mercier, Etude des hydroperoxydes formes par autoxydation de l’oleate de méthyle, et, mise en evidence d’hydroperoxydes cis-a-ethyléniques, Comp. Rend. Acad. Sci. Paris 269:1002 (1969).
M. Piretti, P. Capella, and V. Pallotta, Contribution to the study of hydroperoxides formation in the course of fats autoxidation. Note 1. Rivista Ital. Sostanze Grasse 46:652 (1969).
R. F. Garwood, B. P. S. Khambay, B. C. L. Weedon, and E. N. Frankel, Allylic hydroperoxides from the autoxidation of methyl oleate, J. Chem. Soc., Chem. Commun. 364 (1977).
E. N. Frankel, W. E. Neff, W. K. Rohwedder, B. P. S. Khambay, R. F. Garwood, and B. C. L. Weedon, Analyses of autoxidized fats by gas chromatography-mass spectrometry: I. Methyl oleate, Lipids 12: 901 (1977).
E. N. Frankel, W. E. Neff, W. K. Rohwedder, B. P. S. Khambay, R. F. Garwood, and B. C. L. Weedon, Analysis of autoxidized fats by gas chromatography-mass spectrometry: II. Methyl linoleate. Lipids 12: 908 (1977).
E. N. Frankel, W. E. Neff, W. K. Rohwedder, B. P. S. Khambay, R. F. Garwood, and B. C. L. Weedon, Analysis of autoxidized fats by gas chromatography-mass spectrometry: III. Methyl linolenate. Lipids 12: 1055 (1977).
E. N. Frankel, W. E. Neff, and T. R. Bessler, Analysis of autoxidized fats by gas chromatography-mass spectrometry. V. Photosensitized oxidation. Lipids 14: 961 (1979).
H. W.-S. Chan and G. Levett, Autoxidation of methyl linolenate. Analyses of methyl hydroxylinolenate isomers by high performance liquid chromatography. Lipids 12: 837 (1977).
E. N. Frankel and W. E. Neff, Analysis of autoxidized fats by gas chromatography-mass spectrometry. IV. Soybean oil methyl esters. Lipids 14: 39 (1979).
C. S. Foote, Photosensitized oxygenation and the role of singlet oxygen, Acc. Chem. Res. 1: 104 (1968).
D. Cobern, J. S. Hobbs, R. A. Lucas, and D. J. Mackenzie, Location of hydroperoxide groups in monohydroperoxides formed by chlorophyll-photosensitized oxidation of unsaturated esters, J. Chem. Soc. (C) 1897 (1966).
H. W.-S. Chan, Photo-sensitized oxidation of unsaturated fatty acid methyl esters. The identification of different pathways. J. Am. Oil Chem. Soc. 54: 100 (1977).
J. Terao and S. Matsushita, Products formed by photosensitized oxidation of unsaturated fatty acid esters, J. Am. Oil Chem. Soc. 54: 234 (1977).
S. Matsushita, Photosensitized oxidation of oils and effects of beta-carotene and tocopherols, Paper presented at International Workshop on “Autoxidation Processes in Food and Related Biological Systems, ” U.S. Army Natick RandD Command, Natick, Ma., October 29–31 (1979).
D. Bellus, Quenchers of singlet oxygen, in “Singlet Oxygen Reactions with Organic Compounds and Polymers,” B. Rânby and J. F. Rabek, eds., John Wiley and Sons, New York (1978).
G. W. Grams, K. Eskins, and G. E. Inglett, Dye-sensitized photooxidation of a-tocopherol, J. Am. Chem. Soc. 94: 866 (1972).
G. W. Grams and G. E. Inglett, Sensitized photooxidation of a-tocopherol and of 2,2,5,7,8-pentamethyl-6-chromanol in ethyl acetate, Lipids 7: 442 (1972).
R. L. Clough, B. G. Yee, and C. S. Foote, Chemistry of singlet oxygen. 30. The unstable primary product of tocopherol photooxidation. J. Am. Chem. Soc. 101: 683 (1979).
E. N. Frankel, W. E. Neff, E. Selke, unpublished work.
W. E. Neff, E. N. Frankel, C. R. Scholfield, and D. Weisleder, High-pressure liquid chromatography of autoxidized lipids. I. Methyl oleate and linoleate, Lipids 13: 415 (1978).
W. E. Neff and E. N. Frankel, High-pressure liquid chromatography of autoxidized lipids. II. Methyl linolenate. Unpublished work.
E. N. Frankel and W. E. Neff, unpublished work.
H. W.-S. Chan and G. Levett, Oxidation of methyl oleate: separation of isomeric methyl hydroperoxyoctadecenoates and methyl hydroxystearates by high performance liquid chromatography, Chem. Ind. (London) 692 (1977).
W. E. Neff and E. N. Frankel, Quantitative analyses of hydro-peroxides by high-pressure liquid chromatography of autoxidized and photosensitized-oxidized fatty esters. Paper presented at ISF-AOCS Congress, New York, April 27-May 1 (1980).
E. N. Frankel, R. F. Garwood, B. P. S. Khambay, and B. C. L. Weedon, Stereochemical synthesis of dienol isomers for mechanistic studies of linoleate autoxidation. Paper presented at 14th World Congress of the International Society of Fat Research, Brighton, England, September 1722 (1978). Abstract 0618.
W. H. Tallent, J. Harris, I. A. Wolff, and R. E. Lundin, (R)13-Hydroxy-cis-9, trans-ll-octadecadienoic acid, the principal fatty acid from Coriaria nepalensis Wall. seed oil, Tetrah. Lett. 4329 (1966).
J. L. Bolland and H. P. Koch, The course of autoxidation reactions in polyisoprenes and allied compounds. IX. The primary thermal oxidation product of ethyl linoleate, J. Chem. Soc. 445 (1945).
S. Bergstrom, On the oxidation of the methyl ester of linoleic acid, Arkiv For Kemi, Mineralogi Och Geologi 21A: 1 (1945).
W. O. Lundberg, J. R. Chipault, and M. J. Richardson, Observations on the mechanism of the autoxidation of methyl linoleate, J. Am. Oil Chem. 26: 109 (1949).
S. Privett, W. O. Lundberg, N. A. Khan, W. E. Tolberg, and D. H. Wheeler, Structure of hydroperoxides obtained from autoxidized methyl linoleate, J. Am. Oil Chem. 30: 61 (1953).
N. A. Khan, W. O. Lundberg, and R. T. Holman, Displacement analysis of lipids. IX. Products of the oxidation of methyl linoleate, J. Am. Chem. Soc. 76: 1779 (1954).
E. N. Frankel, Autoxidation, in “Fatty Acids,” E. H. Pryde, ed., AOCS Monograph, American Oil Chemists’ Society, Champaign, Ill. (1979).
G. O. Schenck, 0.-A. Neumuller, and W. Eisfeld, A5-Steroid-7ahydroperoxyde and-7-Ketone durch allylumlagerung von A6steroid-5-u-hydroperoxyden, Justus Liebigs Am. Chem. 618: 202 (1958).
W. F. Brill, The isolation and rearragement of pure acyclic allylic hydroperoxides, J. Am. Chem. Soc. 87: 3286 (1965).
H. W.-S. Chan, G. Levett, and J. A. Matthew, The mechanism of the rearrangement of linoleate hydroperoxides, Chem. Phys. Lipids 24:245 (1979).
P. Haverkamp Begemann, W. J. Woestenburg, and S. Leer, Structure of four methyl linolenate diperoxides, J. Agric. Food Chem. 16:679 (1968).
W. A. Pryor, J. P. Stanley, and E. Blair, Autoxidation of polyunsaturated fatty acids: II. Suggested mechanism for the formation of TBA-reactive materials from prostaglandin-like endoperoxides, Lipids 11: 370 (1976).
N. A. Porter, M. O. Funk, D. Gilmore, R. Isaac, and J. Nixon, The formation of cyclic peroxides from unsaturated hydro-peroxides: models for prostaglandin biosynthesis, J. Am. Chem. Soc. 98: 6000 (1976).
J. E. Baldwin, Rules for ring closure, J. Chem. Soc. Chem. Comm. 734 (1976).
V. P. Maier and A. L. Tappel, Products of unsaturated fatty acid oxidation catalyzed by hematin compounds, J. Am. Oil Chem. Soc. 36: 12 (1959).
H. W. Gardner, Decomposition of linoleic acid hydroperoxides. Enzymic reactions compared with nonenzymic. J. Agric. Food Chem. 23:129 (1975).
H. W. Gardner, D. Weisleder, and R. Kleiman, Formation of trans-12,13-epoxy-9-hydroperoxy-trans-10-octadecenoic acid from 13 L-hydroperoxy-cis-9,trans-l1-octadecadienoic acid catalyzed by either a soybean extract or cysteine-FeC13, Lipids 13: 246 (1978).
P. A. T. Swoboda and K. E. Peers, trans-4,5-epoxyhept-trans-2enal. The major volatile compound formed by the copper and a-tocopherol induced oxidation of butterfat, J. Sci. Fd. Agric. 29: 803 (1978).
E. Selke, W. K. Rohwedder, and H. J. Dutton, Volatile components from trilinolein heated in air, J. Am. Oil Chem. Soc., in press.
S. Patton, I. J. Barnes, and L. E. Evans, n-Deca2,4-dienal. Its origin from linoleate and flavor significance in fats, J. Am. Oil Chem. Soc. 36: 280 (1959).
H. T. Badings, Principles of autoxidation processes in lipids with special regard to the development of autoxidized off-flavors, Neth. Milk Dairy J. 14:215 (1960).
A. M. Gaddis, R. Ellis, and G. T. Currie, Carbonyl in oxidizing fats. V. The composition of neutral volatile monocarbonyl compounds from autoxidized oleate, linoleate, linolenate esters, and fats, J. Am. Oil Chem. Soc. 38: 371 (1961).
C. A. Riely, G. Cohen, and M. Lieberman, Ethane evolution: a new index of lipid peroxidation, Science 183: 208 (1974).
C. J. Dillard, E. E. Dumelin, and A. L. Tappel, Effect of dietary vitamin E on expiration of pentane and ethane by the rat, Lipids 12: 109 (1977).
D. G. Haferman and W. G. Hoekstra, Protection against carbon tetrachloride induced lipid peroxidation in the rat by dietary vitamin E, selenium, and methionine as measured by ethane evolution, J. Nutrit. 107: 656 (1977).
W. G. Hoekstra, Stimulation of and protection against lipid peroxidation in animals in vivo, Paper presented at International Workshop on “Autoxidation Processes in Food and Related Biological Systems, ” U.S. Army Nattick R and D Command, Natick, Ma., October 29–31 (1979).
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Frankel, E.N. (1980). Analytical Methods Used in the Study of Autoxidation Processes. In: Simic, M.G., Karel, M. (eds) Autoxidation in Food and Biological Systems. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-9351-2_9
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DOI: https://doi.org/10.1007/978-1-4757-9351-2_9
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