Abstract
The formation of stable hydroxy derivatives from hydroperoxides produced during the oxidation of linoleic acid methyl ester and fish oil were studied by reverse-phase high-performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS) and 13C nuclear magnetic resonance (NMR) spectroscopy. The oxidation products identified were mixtures of four isomeric hydroxy derivatives: 13-hydroxy-9-cis,11-trans-octadecadienoic, 13-hydroxy-9-trans,11-trans-octadecadienoic, 9-hydroxy-10-trans,12-cis-octadecadienoic, and 9-hydroxy-10-trans,12-trans-octadecadienoic acids. The presence of hydroxy compounds was confirmed by 13C NMR, which gave rise to a hydroxy carbon peak at 87 ppm, and by GC-MS, which showed three peaks corresponding to isomeric mixtures of trimethylsilyl ethers of the oxidized linoleic acid methyl ester. The mass spectra scans of the three peaks showed that they represent isomers of molecular weight 382 and are consistent with the molecular formula C22H42O3Si. In oil extracted from stored frozen mackerel, 13-hydroxy-9-cis,11-trans-octadecadienoic acid was more prominent compared to the model lipid systems. HPLC offered a sensitive means of detection of hydroxy compounds produced both in the initiation and latter stages of oxidation. The effect of antioxidants added to the fish mince prior to storage can also be monitored by HPLC. Thus, the monitoring of lipid oxidation hydroxy derivatives by HPLC is of practical value in the efficient processing and quality control of fish, fish oils, and other fatty foodstuffs in order to enhance the acceptability, nutritional, and safety aspects.
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References
Doll, R., and J. Peto, The Causes of Cancer of Quantitative Estimated of Avoidable Risks of Cancer in the United States Today, J. Natl. Cancer Inst. 66:1192–1308 (1981).
Kinlen, L.J., Fat and Cancer, Br. Med. J. 286:1081–1082 (1983).
Fink, D.J., and D. Kritdhessky, Introduction to the Workshop on Fat and Cancer, Closing Remarks, Cancer Res. 41:3677–3825 (1981).
Shamberger, R.J., in Autoxidation in Food and Biological Systems, edited by M.G. Simic and M. Karel, Plenum Press, New York, 1980, pp. 639–649.
Reddy, B.S., Nutritional Factors and Colon Cancer, Crit. Rev. Food Sci. Nutr. 35:175–190 (1995).
Floyd, R.A., in Free Radicals in Biology, edited by W.A. Pryor, Academic Press, New York, Vol. 4, 1981, pp. 187–206.
Cutler, M.G., and R. Schneider, Tumors and Hormonal Changes Produced in Rats by Subcutaneous Injections of Linoleic Acid Hydroperoxides, Food Cosmet. Toxicol. 12:451–459 (1974).
Bischoff, F., Carcinogenic Effect of Steroids, Adv. Lipid. Res. 7:165–237 (1969).
Petrakis, N.L., L.D. Gruevenke, and T.C. Craig, Cholesterol and Cholesterol Epoxides in Nipple Aspirates of Human Breast Fluid, Cancer Res. 41:2563–2565 (1981).
Black, H.S., and D.R. Douglas, A Model System for the Evaluation of the Role of Cholesterol α-Oxide in Ultraviolet Carcinogenesis, Ibid.:2630–2632 (1972).
Imai, H., N.T. Werthessen, V. Subramanyam, P. Lequesne, W.A.H. Soloway, and M. Kanisawa, Angiotoxicity of Oxygenated Sterols and Possible Precursors, Science 207:651–653 (1980).
Levin, D.E., M. Hollstein, M.F. Chistman, E. Schweiss, and B.N. Ames, A New Salmonella Tester Strain (TA 102) with AT Base-Pairs at the Site of Mutation Detects Oxidative Mutagens, Proc. Natl. Acad. Sci. USA 79:7445–7449 (1982).
Corongiu, F.P., and S. Banni, Detection of Conjugated Dienes by 2nd Derivative Ultraviolet Spectrophotometry, Methods Enzymol. 233:303–310 (1994).
Jessup, W., R.T. Dean, and J.M. Gebicki, Iodometric Determination of Hydroperoxides in Lipids and Proteins, Ibid.:289–303 (1994).
O’Gara, C.Y., K.M. Rao, and L.J. Marnett, A Sensitive Electrochemical Method for Quantitative Hydroperoxide Determination, Chem. Res. Toxicol. 2:295–300 (1989).
Kinter, M., Analytical Technologies for Lipid Oxidation-Products Analysis, J. Chrom. B-Biomed. Appl. 671:223–236 (1995).
Bligh, E.G., and W.J. Dyer, Lipid Extraction from Fish Muscle, Can. J. Biochem. Physiol. 37:911–913 (1959).
Schmarr, H.G., H.B. Gross, and T. Shabamoto, Analysis of Polar Cholesterol Oxidation Products, Evaluation of a New Method Involving Transesterification. Solid-Phase Extraction and Gas Chromatography, J. Agric. Food Chem. 44:512–517 (1996).
Neff, W.E., E.N. Frankel, and D. Weisleder, Photosensitized Oxidation of Methyl Linoleate Secondary Products, Lipids 17:780–790 (1982).
Chan, H.W.S., and G. Levett, Autoxidation of Methyl Linoleate: Analysis of Methyl Hydroxy Linoleate Isomers by High-Performance Liquid Chromatography, Ibid.:837–840 (1977).
Frankel, E.N., W.E. Neff, and E. Seike, Analysis of Auto-Oxidized Fats by GCMS. 7. Volatile Thermal Decomposition Products of Pure Hydroperoxides from Auto-Oxidized and Photosensitized Oxidized Methyl Oleate, Linoleate, and Linolenate, J. Am. Oil Chem. Soc. 58:598–603 (1981).
Porter, N.E., B.A. Weber, H. Weenen, and J.A. Khan, Autoxidation of Polyunsaturated Lipids. Factors Controlling the Steriochemistry of Product Hydroperoxides, J. Am. Chem. Soc. 102:5597–5601 (1980).
Porter, N.A., J. Logan, and V. Kontoyianniday, Preparation and Purification of Arachidonic Acid Hydroperoxides of Biological Importance, J. Org. Chem. 44:3177–3181 (1979).
Frankel, E.N., W.E. Neff, and T.R. Bessler, Analysis of Autoxidized Fats by Gas Chromatography-Mass Spectroscopy: V. Photosensitized Oxidation, Lipids 14:961–967 (1979).
Zhang, A., and Z.Y. Chen, Oxidative Stability of Conjugated Linoleic Acids Relative to Other Polyunsaturated Fatty Acids, J. Am. Oil Chem. Soc. 74:1611–1613 (1997).
Kritharides, L., W. Jessup, J. Gifford, and R.T. Dean, A Method for Defining the Stages of Low-Density Lipoprotein Oxidation by the Separation of Cholesterol and Cholesteryl Ester-Oxidation Products Using HPLC, Anal. Biochem. 213:79–89 (1993).
Brooks, J.W., G. Steel, J.D. Gilbert, and W.A. Harland, Lipids of Human Atheroma, Atheroscherosis 13:223–237 (1971).
Wang, T., W.G. Yu, and W.S. Powell. Formation of Monohydroxy Derivatives of Arachidonic Acid, Linoleic Acid and Oleic Acid During Oxidation of Low Density Lipoprotein by Copper Ions and Endothelial Cells, J. Lipid Res. 33:525–537 (1992).
Jerra, W., and G. Spiteller, Increase in Hydroxy Fatty Acids in Human Low Density Lipoproteins with Age, Chem. Phys. Lipids 84:165–173 (1996).
Spiteller, P., and G. Spiteller, 9-Hydroxy-10,12-octadecadienoic Acid (9-HODE) and 13-Hydroxy-9,11-octadecadienoic Acid (13-HODA), Excellent Markers for Lipid Peroxidation, Ibid.:131–139 (1997).
Jerra, W., G. Spiteller, W. Carson, and A. Schamm, Strong Increase in Hydroxy Fatty Acids Derived from Linoleic Acid in Human Low Density Lipoproteins of Atherosclerosis Patients, Ibid.:1–11 (1998).
Brooks, C.J.W., W.A. Harland, G. Steel, and J.D. Gilbert, Lipids of Human Atheroma: Isolation of Hydroxyoctadecadienoic Acids from Advanced Aortal Lesions, Biochim. Biophys. Acta 202:563–566 (1970).
Harland, W.A., J.D. Gilbert, and C.J.W. Brooks, Lipids of Human Atheroma. VIII. Oxidized Derivatives of Cholesteryl Linoleate, Ibid.:378–385 (1973).
Belkner, J., R. Wiesner, H. Kuhn, and V.Z. Lankin, The Oxygenation of Cholesterol Esters by the Reticulocyte Lipoxygenase, FEBS Lett. 279:110–114 (1991).
Kuhn, H., J. Belkner, R. Wiesner, T. Schewe, V.Z. Lankin, and A.K. Tikhaze, Structure Elucidation of Oxygenated Lipids in Human Atherosclerotic Lesions, Eicosanoids 5:17–22 (1992).
Blankenhorn, D.H., R.L. Johnson, W.J. Mack, H.A. El Zain, and L.I. Vailas, The Influence of Diet on the Appearance of New Lesions in Human Coronary Arteries, J. Am. Med. Assoc. 263:1646–1652 (1990).
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Saeed, S., Howell, N.K. High-performance liquid chromatography and spectroscopic studies on fish oil oxidation products extracted from frozen atlantic mackerel. J Amer Oil Chem Soc 76, 391–397 (1999). https://doi.org/10.1007/s11746-999-0247-4
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DOI: https://doi.org/10.1007/s11746-999-0247-4