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Tentative identification and quantification of TAG core aldehydes as dinitrophenylhydrazones in autoxidized sunflowerseed oil using reversed-phase HPLC with electrospray lonization MS

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Lipids

Abstract

The molecular species of TAG core aldehydes (aldehydes still esterified to parent molecules) were detected and quantified in dietary-quality sunflowerseed oil autoxidized for 0‐18 d at 60°C in the dark. The analyses were performed by reversed-phase HPLC with UV (358 nm) absorption or light scattering and electrospray ionization-MS (ESI/MS) detection following preparation of the dinitrophenylhydrazone derivatives. Aldehyde production, as estimated by UV and ESI/MS, increased gradually over the 18-d period following a rapid initial destruction of the core aldehydes accumulated during storage of the commercial oil at 10°C for 3 mon. The contents of hydroperoxides and hydroperoxide core aldehyde combinations were estimated to account for about 5% of total TAG, quantified as area in the chromatographic trace, after 18 d of autoxidation as estimated by an evaporative light scattering detector (ELSD). The major species of core aldehydes were tentatively identified as 9-oxononanoyl (70%)-, 12-oxo-9,10-epoxydodecenoyl (10%)-, and 13-oxo-9,11-tridecadienoyl (5%)-containing acylglycerols, plus smaller amounts of simple and mixed chain-length dialdehydes, and hydroxy and epoxy monoaldehyde-containing acylglycerols (15% of total). Quantitatively, the core aldehydes made up 2–12 g/kg of oil by UV detection and 2–9 g/kg of oil by EsI/MS detection, whereas the hydroperoxides measured in the unreduced state by HPLC with ELSD were estimated at 200 g/kg after 18 d of autoxidation. The major hydroperoxides of sunflowerseed oil were as previously identified.

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Abbreviations

ALD:

aldehyde

DNPH:

2,4-dinitrophenylhydrazone

ELSD:

evaporative light-scattering detector

ESI:

electrospray ionization

KET:

ketone

HPLC:

reversed-phase HPLC

TBHP:

tert-butyl hydroperoxide

References

  1. Frankel, E.N. (1984) Lipid Oxidation: Mechanism, Products, and Biological Significance, J. Am. Oil Chem. Soc. 61, 908–1917.

    Google Scholar 

  2. Porter, N.A., Caldwell, S.E., and Mills, K.A. (1995) Review. Mechanisms of Free Radical Oxidation of Unsaturated Lipids, Lipids 30, 277–290.

    PubMed  CAS  Google Scholar 

  3. Frankel, E.N. (1985) Chemistry of Free Radical and Singlet Oxidation of Lipids, Prog. Lipid Res. 23, 197–221.

    Article  Google Scholar 

  4. Esterbauer, H., Zollner, H., and Schauer, 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, FL.

    Google Scholar 

  5. Kuksis, A. (1990) Core Aldehydes—Neglected Products of Lipid Peroxidation. INFORM 1, 1055–1060.

    Google Scholar 

  6. Halliwell, B., and Gutteridge, J.M.C. (1989) Free Radicals in Biology and Medicine, 2nd edn., pp. 1–20. Clarendon Press, Oxford, United Kingdom.

    Google Scholar 

  7. Kuksis, A., Myher, J.J., Marai, L., and Geher, K. (1993) Analyses of Hydroperoxides and Core Aldehydes of Triacylglycerols, in Proceedings of 17th Nordic Lipid Symposium (Mälkki, Y., ed.), pp. 230–238. Lipidforum, Bergen, Norway.

    Google Scholar 

  8. Kamal-Eldin, A., Marquez-Ruiz, G., Dobarganes, C., and Appelqvist, L.-A. (1997) Characterisation of Aldehydic Acids in Used and Unused Frying Oils, J. Chromatogr. A 776, 245–254.

    Article  CAS  Google Scholar 

  9. 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.

    CAS  Google Scholar 

  10. 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.

    Article  PubMed  Google Scholar 

  11. Byrdwell, W.C., and Neff, W.E. (2001) Autoxidation Products of Normal and Genetically Modified Canola Oil Varieties Determined Using Liquid Chromatography with Mass Spectrometric Detection, J. Chromatogr. A 905, 85–102.

    Article  PubMed  CAS  Google Scholar 

  12. Berdeaux, O., Velasco, J., Márquez-Ruiz, G., and Dobarganes, C. (2002) Evolution of Short-Chain Glycerol-Bound Compounds During Thermooxidation of FAME and Monoacid TAG, J. Am. Oil Chem. Soc. 79, 279–285.

    CAS  Google Scholar 

  13. Sjövall, O., Kuksis, A., and Kallio, H. (2002) Formation of Triacylglycerol Core Aldehydes During Rapid Oxidation of Corn and Sunflower Oils with tert-Butyl Hydroperoxide/Fe2+, Lipids 37, 81–94.

    Google Scholar 

  14. 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.

    CAS  Google Scholar 

  15. Sjovall, O., Kuksis, A., Marai, L., and Myher, J.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.

    Article  PubMed  CAS  Google Scholar 

  16. Chiba, T., Takazawa, M., and Fujimato, K. (1989) A Simple Method for Estimating Carbonyl Content in Peroxide-Containing Oils, J. Am. Oil Chem. Soc. 66, 1588–1592.

    CAS  Google Scholar 

  17. Kamido, H., Kuksis, A., Marai, L., Myher, J.J., and Pang, H. (1992) Preparation, Chromatography and Mass Spectrometry of Cholestery Ester and Glycerolipid-Bound Aldehydes, Lipids 27, 645–650.

    CAS  Google Scholar 

  18. IUPAC, International Union of Pure and Applied Chemistry, Applied Chemistry Division. Commission on Oils, Fats and Derivatives (1987) Standard Methods for the Analysis of Oils, Fats and Derivatives, 7th rev. enlarged edn. (Paquot, C., and Hautfenne, A., eds.), Blackwell Scientific Publications, Oxford, United Kingdom.

    Google Scholar 

  19. AOCS, Official Methods and Recommended Practices of the American Oil Chemists' Society, 5th edn., AOCS Press, Champaign, 1997.

    Google Scholar 

  20. Myher, J.J., Kuksis, A., and Pind, S. (1989) Molecular Species of Glycerophospholipids and Sphingomyelins of Human Erythrocytes: Improved Method of Analysis, Lipids 24, 396–407.

    PubMed  CAS  Google Scholar 

  21. Podrez, E.A., Poliakov, E., Shen, Z., Zhang, R., Deng, Y., Sun, M., Finton, P.J., Shan, L., Gugiu, B., Fox, P.L., et al. (2002). Identification of a Novel Family of Oxidized Phospholipids That Serve as Ligands for the Macrophage Scavenger Receptor CD 36, J. Biol. Chem. 277, 38503–38516.

    Article  PubMed  CAS  Google Scholar 

  22. Frankel, E.N. (1998) Lipid Oxidation, The Oily Press, Dundee, Scotland.

    Google Scholar 

  23. Frankel, E.N. (1980) Lipid Oxidation, Prog. Lipid Res. 19, 1–22.

    Article  PubMed  CAS  Google Scholar 

  24. Byrdwell, W.C., and Neff, W.E. (2002) Dual Parallel Electrospray Ionization and Atmospheric Pressure Chemical Ionization Mass Spectrometry (MS), MS/MS and M/MS/MS for the Analysis of Triacylglycerols and Triacylglycerol Oxidation Products, Rapid Commun. Mass Spectrom. 16, 300–319.

    Article  PubMed  CAS  Google Scholar 

  25. Byrdwell, W.C., and Neff, W.E. (1999) Non-volatile Products of Triolein Produced at Frying Temperatures Characterized Using Liquid Chromatography with On-line Mass Spectrometric Detection, J. Chromatogr. A 852, 417–432.

    Article  PubMed  CAS  Google Scholar 

  26. Friedman, P., Horkko, S., Steinberg, D., Witzum, J.L., and Dennis, E.A. (2002) Correlation of Antiphospholipid Antibody Recognition with the Structure of Synthetic Oxidized Phospholipids. Importance of Schiff Base Formation and Aldol Condensation, J. Biol. Chem. 277, 7010–7020.

    Article  PubMed  CAS  Google Scholar 

  27. 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.

    PubMed  CAS  Google Scholar 

  28. Hopia, A. (1994) Estimation of the Oxidation Level of Edible Oils: High Performance Size-Exclusion Chromatography (HPSEC) Applied to the Early Phase of Oxidation, Ph.D. Dissertation, University of Helsinki, Department of Applied Chemistry and Microbiology, Yliopistopaino, Helsinki, Finland.

    Google Scholar 

  29. 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.

    Article  PubMed  CAS  Google Scholar 

  30. Kurvinen, J.-P., Kuksis, A., Ravandi, A., Sjövall, O., and Kallio, H. (1999) Rapid Complexing of Oxoaxcylglycerols with Amino Acids, Peptides, and Aminophospholipids, Lipids 34, 299–305.

    Article  PubMed  CAS  Google Scholar 

  31. Grzelinska, E., Bartosz, G., Gwozdzinski, K., and Ieyko, 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.

    CAS  Google Scholar 

  32. Kanazawa, K., and Ashida, H. (1998) Catabolic Fate of Dietary Trilinoleoylglycerol Hydroperoxides in Rat Gastrointestines, Biochim. Biophys. Acta 1393, 336–348.

    PubMed  CAS  Google Scholar 

  33. 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.

    PubMed  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Biochemistry and Food Chemistry, FIN-20014 University of Turku, Finland

    Olli Sjövall & Heikki Kallio

  2. Banting and Best Department of Medical Research, University of Toronto, Charles H. Best Institute, 112 College St., M5G 1L6, Toronto, Canada

    Olli Sjövall & Arnis Kuksis

Authors
  1. Olli Sjövall
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  2. Arnis Kuksis
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  3. Heikki Kallio
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Correspondence to Arnis Kuksis.

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Sjövall, O., Kuksis, A. & Kallio, H. Tentative identification and quantification of TAG core aldehydes as dinitrophenylhydrazones in autoxidized sunflowerseed oil using reversed-phase HPLC with electrospray lonization MS. Lipids 38, 1179–1190 (2003). https://doi.org/10.1007/s11745-003-1177-7

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  • DOI: https://doi.org/10.1007/s11745-003-1177-7

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