Abstract
The lipid ester core aldehydes formed during a rapid oxidation (7.8 M tert-butyl hydroperoxide, 90 min at 37°C) of the triacylglycerols of purified corn and sunflower oils were isolated as dinitrophenylhydrazones by preparative thin-layer chromatography and identified by reversed-phase high-performance liquid chromatography with on-line electrospray ionization mass spectrometry and by reference to standards. A total of 113 species of triacylglycerol core aldehydes were specifically identified, accounting for 32–53% of the 2,4-dinitrophenylhydrazine (DNPH)-reactive material of high molecular weight representing 25–33% of the total oxidation products. The major core aldehyde species (50–60% of total triacylglycerol core aldehydes) were the mono(9-oxo)nonanoyl- and mono(12-oxo)-9,10-epoxy dodecenoyl- or (12-oxo)-9-hydroxy-10,11-dodecenoyl-diacylglycerols. A significant proportion of the total (9-oxo)nonanoyl and epoxidized (12-oxo)-9,10-dodecenoyl core aldehydes was found in complex combinations with hydroperoxy or hydroxy fatty acyl groups (6–10% of total triacylglycerol core aldehydes). Identified were also di(9-oxo)nonanoylmonoacylglycerols (0.5% of total) and tri(9-oxo)nonanoylglycerols (trace). The identification of the oxoacylglycerols was consistent with the products anticipated from tert-butyl hydroperoxide oxidation of the major species of corn and sunflower oil triacylglycerols (mainly linoleoyl esters). However, the anticipated (13-oxo)-9,11-tridecadienoyl aldehyde-containing acylglycerols were absent because of further oxidation of the dienoic core aldehyde. A significant proportion of the unsaturated triacylglycerol core aldehydes contained tert-butyl groups linked to the unsaturated fatty chains via peroxide bridges (2–9%). The study demonstrates that rapid peroxidation with tert-butyl hydroperoxide consitutes an effective method for enriching natural oils and fats in triacylglycerol core aldehydes for biochemical and metabolic testing.
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Abbreviations
- ALD:
-
aldehyde
- CI:
-
chemical ionization
- CID:
-
collision-induced dissociation
- DLI:
-
direct liquid inlet
- DNPH:
-
2,4-dinitrophenylhydrazine
- EI:
-
electron impact
- ESI:
-
electrospray ionization
- HPLC:
-
high-performance liquid chromatography
- LC:
-
liquid chromatography
- M:
-
molecular ion
- MS:
-
mass spectrometry
- LC:
-
liquid chromatography
- M:
-
molecular ion
- MS:
-
mass spectrometry
- Rt:
-
retention time
- TBHP:
-
tert-butyl hydroperoxide
- TCN:
-
theoretical carbon number
- TLC:
-
thin-layer chromatography
References
Frankel, E.N. (1984) Lipid Oxidation: Mechanism, Products, and Biological Significance, J. Am. Oil Chem. Soc. 61, 1908–1917.
Porter, N.A., Caldwell, S.E., and Mills, K.A. (1995) Mechanisms of Free Radical Oxidation of Unsaturated Lipids, Lipids 30, 277–290.
Frankel, E.N. (1985) Chemistry of Autoxidation: Mechanism, Products, and Flavor Significance, in Flavor Chemistry of Fats and Oils (Min, D., and Smouse, T.H., eds.), pp. 1–37, American Oil Chemists' Society, Champaign.
Lee, I., Fatemi, S.H., Hammond, E.G., and White, P.J. (1995) Quantitation of Flavour Volatiles in Oxidized Soybean Oil by Dynamic Headspace Analysis, J. Am. Oil Chem. Soc. 72, 539–546.
Kuksis, A. (1990) Core Aldehydes—Neglected Products of Lipid Peroxidation, inform 1, 1055–1058.
Esterbauer, H., Zollner, H., and Schauers, R.S. (1989) Aldehydes Formed by Lipid Peroxidation: Mechanism of Formation, Occurrence, and Determination, in Membrane Lipid Oxidation (Vigo-Pelfrey, C., ed.), Vol. 1, pp. 239–268, CRC Press, Boca Raton.
Brunner, B.A., Jones, A.D., and German, J.B. (1995) Direct Characterization of Protein Adducts of the Lipid Peroxidation Product 4-Hydroxynonenal Using Electroaspray Mass Spectrometry, Chem. Res. Toxicol. 8, 552–559.
Bolgar, M.S., Yang, C., and Gaskell, S.J. (1996) First Direct Evidence for Lipid/Protein Conjugation in Oxidized Human Low Density Lipoprotein, J. Biol. Chem. 271, 27999–28001.
Fogelman, A.M., Schechter, I., Saeger, J., Hokum, M., Child, J.S., and Edwards, P.A. (1980) Malonaldehyde Alteration of Low Density Lipoproteins Leads to Cholesteryl Ester Accumulation in Human Monocyte-Macrophages, Proc. Natl. Acad. Sci. USA 77, 2214–2218.
Kaneko, T., Kaji, K., and Matsuo, M. (1988) Cytotoxicities of a Linoleic Acid Hydroperoxide and Its Related Aliphatic Aldehydes Toward Cultured Human Umbilical Vein Endothelial Cells, Chem. Biol. Interact. 67(3–4), 295–304.
Szweda, L.I., Uchida, K., Tsai, L., and Stadtman, E.R. (1993) Inactivation of Glucose-6-Phosphate Dehydrogenase by 4-Hydroxy 2-Nonenal. Selective Modification of an Active Site Lysine, J. Biol. Chem. 268, 3342–3347.
Grzelinska, E., Bartosz, G., Gwozdzinski K., and Leyko, W. (1979) A Spin-Label Study of the Effect of γ-Radiation on Erythrocyte Membrane. Influence of Lipid Peroxidation on Membrane Structure, Int. J. Radiat. Biol. 36, 325–334.
Ravandi, A., Kuksis, A., Shaikh, N., and Jackowski, G. (1997) Preparation of Schiff Base Adducts of Phosphatidylcholine Core Aldehydes and Aminophospholipids, Amino Acids, and Myoglobin, Lipids 32, 989–1001.
Kurvinen, J.-P., Kuksis, A., Ravandi, A., Sjövall, O., and Kallio, H. (1999) Rapid Complexing of Oxoacylglycerols with Amino Acids, Peptides, and Aminophospholipids, Lipids 34, 299–305.
Kanazawa, K., and Ashida, H. (1998) Dietary Hydroperoxides of Linoleic Acid Decompose to Aldehydes in Stomach Before Being Absorbed into the Body, Biochim. Biophys. Acta 1393, 349–361.
Kanazawa, K., and Ashida, H. (1998) Catabolic Fate of Dietary Trilinoleoglycerol Hydroperoxides in Rat Gastrointestines, Biochim. Biophys. Acta 1393, 336–348.
Naruszewicz, M., Wozny, E., Mirkiewicz, G., Nowicka, G., and Szostak, W.B. (1987) The Effect of Thermally Oxidized Soya Bean Oil on Metabolism of Chylomicrons: Increased Uptake and Degradation of Oxidized Chylomicrons in Cultured Mouse Macrophages, Atherosclerosis 66, 45–53.
Staprãns, I., Rapp, J.H., Pan, X.-M., Kim, K.Y., and Feingold, K.R. (1994) Oxidized Lipids in the Diet Are a Source of Oxidized Lipid in Chylomicrons of Human Serum, Arterioscler. Thromb. 14, 1900–1905.
Kamido, H., Kuksis, A., Marai, L., Myher, J.J., and Pang, H. (1992) Preparation, Chromatography, and Mass Spectrometry of Cholesteryl Ester and Glycerolipid-Bound Aldehydes, Lipids 27, 645–650.
Kamido, H., Kuksis, A., Marai, L., and Myher, J.J. (1993) Identification of Core Aldehydes Among in vitro Peroxidation Products of Cholesteryl Esters, Lipids 28, 331–336.
Kuksis, A., Myher, J.J., Marai, L., and Geher, K. (1993) Analyses of Hydroperoxides and Core Aldehydes of Triacylglycerols, in 17th Nordic Lipid Symposium, Lipidforum (Mälkki, Y., ed.), pp. 230–238, Bergen, Norway.
Sjövall, O., Kuksis, A., Marai, L., and Myher, J. (1997) Elution Factors of Synthetic Oxotriacylglycerols as an Aid in Identification of Peroxidized Natural Triacylglycerols by Reversed-Phase High-Performance Liquid Chromatography with Electrospray Mass Spectrometry, Lipids 32, 1211–1218.
Duffin, K.L., Henion, J.D., and Shieh, J.J. (1991) Electrospray and Tandem Mass Spectrometric Characterization of Acylglycerol Mixtures That Dissolved in Nonpolar Solvents, Anal. Chem. 63, 1781–1788.
Myher, J.J., and Kuksis, A. (1995) Electrospray-MS for Lipid Identification, inform 6, 1068–1072.
Marai, L., Myher, J.J., and Kuksis, A. (1983) Analysis of Triacylglycerols by Reversed-Phase High Pressure Liquid Chromatography with Direct Liquid Inlet Mass Spectrometry, Can. J. Biochem. Cell Biol. 61, 840–849.
Reske, J., Siebrecht, J., and Hazebroek, J. (1997) Triacylglycerol Composition and Structure in Genetically Modified Sunflower and Soybean Oils, J. Am. Oil Chem. Soc. 74, 989–998.
Sjövall, O., Kuksis, A., and Kallio, H. (2001) Regioisomers of Octanoic Acid-Containing Structured Triacylglycerols Analyzed by Tandem Mass Spectrometry Using Ammonia Negative Chemical Ionization, Lipids 36, 1377–1382.
Halliwell, B., and Gutteridge, J.M.C. (1989) Free Radicals in Biology and Medicine, pp. 210–214, Clarendon Press, Oxford.
Gardner, H.W. (1989) Oxygen Radical Chemistry of Polyunsaturated Fatty Acids, Free Radic. Biol. Med. 7, 65–86.
Porter, N.A. (1992) Alkyl Hydroperoxides in Organic Peroxides (Ando, W., ed.), pp. 101–156, John Wiley & Sons, Chichester.
Miyashita, K., Hara, N., Fujimoto, K., and Kaneda, T. (1985) Dimers Formed in Oxygenated Methyl Linoleate Hydroperoxides, Lipids 20, 578–587.
Brash, A.R. (2000) Autoxidation of Methyl Linoleate: Identification of the Bis-allylic 11-Hydroperoxide, Lipids 35, 947–952.
Frankel, E.N. (1980) Lipid Oxidation, Prog. Lipid Res. 19, 1–22.
Gardner, H.W. (1991) Recent Investigations into the Lipoxygenase Pathway of Plants, Biochim. Biophys. Acta 1084, 221–239.
Frankel, E.N., Neff, W.E., Rohwedder, W.K., Khambay, B.P.S., Garwood, R.F., and Weedon, B.C.L. (1977). Analysis of Autoxidized Fats by Gas Chromatography-Mass Spectrometry: I. Methyl Oleate, Lipids 12, 901–907.
Gardner, H., Weisleder, D., and Kleiman, R. (1978) Formation of trans-12,13-Epoxy-9-Hydroperoxy-trans-10-Octadecenoic Acid from 13-l-Hydroperoxy-cis-8,trans-11-octadecadienoic Acid Catalyzed by Either a Soybean Extract or Cysteine-FeCl3, Lipids 13, 246–252.
Noordermeer, M.A., Feussner, I., Kolbe, A., Veldink, G.A., and Vliegenthart, J.F.G. (2000) Oxygenation of (3Z)-Alkenals to 4-Hydroxy-(2E)-Alkenals in Plant Extracts: A Nonenzymatic Process, Biochem. Biophys. Res. Commun. 277, 112–116.
Piazza, G., Foglia, T., and Nuñez, A. (2001) Epoxidation of Carbon-Carbon Double Bonds in Fatty Acids and Other Compounds with Membrane-Supported Peroxygenase, in 92nd AOCS Annual Meeting & Expo Abstracts, Minneapolis, Minnesota (Abstract S80).
Hughes, H., Smith, C.V., Horning, E.C., and Mitchell, J.R. (1983) High-Performance Liquid Chromatography and Gas Chromatography-Mass Spectrometry Determination of Specific Lipid Peroxidation Products in vivo, Anal. Biochem. 130, 431–436.
Porter, N.A., Wolf, R.A., and Weenen, H. (1979) The Free Radical Oxidation of Polyunsaturated Lecithins, Lipids 15, 164–167.
Park, D.K., Terao, J., and Matsushita, S. (1981) High-Performance Liquid Chromatography of Hydroperoxides Formed by Autoxidation of Vegetable Oils, Agric. Biol. Chem. 45, 2443–2448.
Steenhorst-Slikkerveer, L., Louter, A., Janssen, H.-G., and Bauer-Plank, C. (2000) Analysis of Nonvolatile Lipid Oxidation Products in Vegetable Oils by Normal-Phase High-Performance Liquid Chromatography with Mass Spectrometric Detection, J. Am. Oil Chem. Soc. 77, 837–845.
Kusaka, T., Ishihara, S., Sakaida, M., Mifune, A., Nakano, Y., Tsuda, K., Ikeda, M., and Nakano, H. (1996) Composition Analysis of Normal Plant Triacylglycerols and Hydroperoxidized rac-1-Stearoyl-2-oleoyl-3-linoleoyl-sn-glycerols by Liquid Chromatography-Atmospheric Pressure Chemical Ionization Mass Spectrometry, J. Chromatogr. A 730, 1–7.
Lin, J.-T., Snyder, L.R., and McKeon, T.A. (1998) Prediction of Relative Retention Times of Triacylglycerols in Non-aqueous Reversed-Phase High-Performance Liquid Chromatography, J. Chromatogr. A 808, 43–49.
Kuklev, D.V., Christie, W.W., Durand, T., Rossi, J.C., Vidal, J.P., Kasyanov, S.P., Akulin, V.N., and Bezuglov, V.V. (1997) Synthesis of Keto- and Hydroxydienoic Compounds from Linoleic Acid, Chem. Phys. Lipid 85, 125–134.
Viinanen, E., and Hopia, A. (1994) Reversed-Phase High-Performance Liquid Chromatographic Analysis of Triacylglycerol Autoxidation Products with Ultraviolet and Evaporative Light-Scattering Detectors, J. Am. Oil Chem. Soc. 71, 537–539.
Sjövall, O., Kuksis, A., and Kallio, H. (2001) Reversed-Phase High-Performance Liquid Chromatographic Separation of tert-Butyl Hydroperoxide Oxidation Products of Unsaturated Triacylglycerols, J. Chromatogr. A 905, 119–132.
Courtneidge, J.L. (1992) Polyfunctional Peroxides from tert-Butyl Hydroperoxide-Loaded Autoxidations of Polyunsaturated Substrates and an Assessment of the Rate Constants for Allylic Peroxyl Radical Ring Closures, J. Chem. Soc., Chem. Commun. 1270–1272.
Yamauchi, R., Hara, Y., Murase, H., and Kato, K. (2000) Analysis of the Addition Products of α-Tocopherol with Phosphatidylcholine-Peroxyl Radicals by High-Performance Liquid Chromatography with Chemiluminescent Detection, Lipids 35, 1405–1410.
Kamal-Eldin, A., Marquez-Ruiz, G., Dobarganes, C., Appelqvist, L-A. (1997) Characterization of Aldehydic Acids in Used and Unused Frying Oils, J. Chromatogr. A 776, 245–254.
Kamido, H., Kuksis, A., Marai, L., and Myher, J.J. (1995) Lipid Ester-Bound Aldehydes Among Copper-Catalyzed Peroxidation Products of Human Plasma Lipoproteins, J. Lipid Res. 36, 1876–1886.
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Sjövall, O., Kuksis, A. & Kallio, H. Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert-butyl hydroperoxide/Fe2+ . Lipids 37, 81–94 (2002). https://doi.org/10.1007/s11745-002-0867-5
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DOI: https://doi.org/10.1007/s11745-002-0867-5