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Quantification of key odorants formed by autoxidation of arachidonic acid using isotope dilution assay

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Lipids

Abstract

Six odor-active compounds generated by autoxidation of arachidonic acid (AA) were quantified by isotope dilution assay (IDA), i.e., hexanal (1), 1-octen-3-one (2), (E,Z)-2,4-decadienal (3), (E,E)-2,4-decadienal (4), trans-4,5-epoxy-(E)-2-decenal (5), and (E,Z,Z)-2,4,7-tridecatrienal (6). Compound 1 was the most abundant odorant with about 700 mg/100 g autoxidized AA, which corresponds to 2.2 mol% yield. Based on the odor activity values (ratio of concentration to odor threshold), odorants 3 (fatty) and 5 (metallic) showed the highest sensory contribution followed by 1 (green), 2 (mushroom-like), 6 (egg white-like), and 4 (fatty). For the first time, reliable quantitative results are reported for odorants 1–6 in autoxidized AA, in particular odorant 6, which is a characteristic compound found in autoxidized AA. Synthesis of deuterated 6, required for IDA, is described in detail. The formation of odorants 1–6 by autoxidation of AA is discussed with respect to the quantitative data.

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Abbreviations

AA:

arachidonic acid

CC:

column chromatography

CI:

chemical ionization

EI:

electron ionization

GC:

gas chromatography

GC-O:

gas chromatography-olfactometry

HPET:

hydroperoxyeicosatrienoic acid

HPETE:

hydroperoxyeicosatetraenoic acid

HPOD:

hydroperoxyoctadecadienoic acid

IDA:

isotope dilution assay

IS:

internal standard

MS:

mass spectrometry

NMR:

nuclear magnetic resonance

OAV:

odor activity value

PCI:

positive chemical ionization

RI:

retention index

SIM:

selected ion monitoring

References

  1. Leaf, A.A., Leighfield, M.J. Costeloe, K.L., and Crawford, M.A. (1992) Long-Chain Polyunsaturated Fatty Acids and Fetal Growth, Early Hum. Dev. 30, 183–191.

    Article  PubMed  CAS  Google Scholar 

  2. Koletzko, B., and Braun, M. (1991) Arachidonic Acid and Early Human Growth: Is There a Relation? Ann. Nutr. Metab. 35, 128–131.

    Article  PubMed  CAS  Google Scholar 

  3. Carlson, S.E., Werkman, S.H., Peeples, J.M., Cooke, R.J., and Tolley, E.A. (1993) Arachidonic Acid Status Correlates with First-Year Growth in Pretern Infants, Proc. Natl. Acad. Sci. USA 90, 1073–1077.

    Article  PubMed  CAS  Google Scholar 

  4. Hempenius, R.A., van Delft, J.M.H., Prinsen, M., and Lina, B.A.R. (1997) Preliminary Safety Assessment of an Arachidonic Acid-Enriched Oil Derived from Mortierella alpina: Summary of Toxicological Data, Food Chem. Toxicol. 35, 573–581.

    Article  PubMed  CAS  Google Scholar 

  5. Frankel, E.N. (1982) Volatile Lipid Degradation Products, Prog. Lipid Res. 22, 1–33.

    Article  Google Scholar 

  6. Grosch, W. (1987) Reactions of Hydroperoxides—Products of Low Molecular Weight, in Autoxidation of Unsaturated Lipids (Chan, H.W.-S., ed.), pp. 95–139, Academic Press, London.

    Google Scholar 

  7. Ellis, R., Gaddis, A.M., and Currie, G.T. (1966) Carbonyls in Oxidized Fat. IX Aldehydes Isolated from Autoxidized Methyl Arachidonate, J. Food Sci. 31, 191–195.

    Article  CAS  Google Scholar 

  8. Badings, H.T. (1970) Cold-Storage Defects in Butter and Their Relation to the Autoxidation of Unsaturated Fatty Acids, Neth. Milk Dairy J. 24, 145–256.

    Google Scholar 

  9. Taylor, A.J., and Mottram, D.S. (1990) Composition and Odour of Volatiles from Autoxidised Methyl Arachidonate. J. Sci. Food Agric. 50, 407–417.

    Article  CAS  Google Scholar 

  10. Artz, W.E., Perkins, E.G., and Salvador-Henson, L. (1993) Characterization of the Volatile Decomposition Products of Oxidized Methyl Arachidonate, J. Am. Oil Chem. Soc. 70, 377–382.

    CAS  Google Scholar 

  11. Blank, I., Lin, J., and Fay, L.B. (2000) Aroma Impact Compounds Formed by Autoxidation of Arachidonic Acid, in Frontiers of Flavour Science (Schieberle, P., and Engel, K.-H., eds.), pp. 3–9, Deutsche Forschungsanstalt für Lebensmittelchemie, Garching.

    Google Scholar 

  12. Blank, I., Lin, J., Arce Vera, F., Welti, D.H., and Fay, L.B. (2001) Identification of Potent Odorants Formed by Autoxidation of Arachidonic Acid—Structure Elucidation and Synthesis of (E.Z.Z.)-2,4,7-Tridecatrienal. J. Agric. Food Chem. 49, 2959–2965.

    PubMed  CAS  Google Scholar 

  13. Schieberle, P., and Grosch, W. (1987) Quantitative Analysis of Aroma Compounds in Wheat and Rye Bread Crusts Using Stable Isotope Dilution Assay, J. Agric. Food Chem. 35, 252–257.

    Article  CAS  Google Scholar 

  14. Guth, H., and Grosch, W. (1990) Deterioration of Soya-Bean Oil: Quantification of Primary Flavour Compounds Using a Stable Isotope Dilution Assay. Lebensm. Wiss. Technol. 23, 513–522.

    CAS  Google Scholar 

  15. Blank, I., Milo, C., Lin, J., and Fay, L.B. (1999) Quantification of Aroma-Impact Compounds by Isotope Dilution Assay—Recent Developments, in Flavor Chemistry: 30 Years of Progress (Teranishi, R., Wick, E.L., and Hornstein, I., eds.), pp. 63–74. Kluwer Academic/Plenum Publishers, New York.

    Google Scholar 

  16. Gassenmeier, K., and Schieberle, P. (1994) Comparison of Important Odorants in Puff-Pastries Prepared with Butter or Margarine. Lebensm. Wiss. Technol. 27, 282–288.

    Article  CAS  Google Scholar 

  17. Grosch, W. (1994) Determination of Potent Odourants in Foods by Aroma Extract Dilution Analysis (AEDA) and Calculation of Odour Activity Values (OAVs), Flav. Fragr. J. 9, 147–158.

    Article  CAS  Google Scholar 

  18. Ullrich, F., and Grosch, W. (1987) Identification of the Most Intense Volatile Flavour Compounds Formed During Autoxidation of Linoleic Acid. Z. Lebensm. Unters. Forsch. 184, 277–282.

    Article  CAS  Google Scholar 

  19. Lin, J., Fay, L.B., Welti, D.H., and Blank, I. (1999) Synthesis of trans-4,5-Epoxy-(E)-2-decenal and Its Deuterated Analog Used for the Development of a Sensitive and Selective Quantification Method Based on Isotope Dilution Assay with Negative Chemical Ionization, Lipids 34, 1117–1126.

    Article  PubMed  CAS  Google Scholar 

  20. Lin, J., Welti, D.H., Arce Vera, F., Fay, L.B., and Blank, I. (1999) Synthesis of Deuterated Volatile Lipid Degradation Products to be Used as Internal Standards in Isotope Dilution Assays. 1. Aldeh6des, J. Agric. Food Chem. 47, 2813–2821.

    Article  PubMed  CAS  Google Scholar 

  21. Lin, J., Welti, D.H., Arce Vera, F., Fay, L.B., and Blank, I. (1999) Synthesis of Deuterated Volatile Lipid Degradation Products to be Used as Internal Standards in Isotope Dilution Assays. 2 Vinyl Ketones, J. Agric. Food Chem. 47, 2822–2829.

    Article  PubMed  CAS  Google Scholar 

  22. Tsoukalas, B., and Grosch, W. (1977) Analysis of Fat Deterioration—Comparison of Some Photometric Tests, J. Am. Oil Chem. Soc. 54, 490–493.

    CAS  Google Scholar 

  23. van den Dool, H., and Kratz, P. (1963) A Generalization of the Retention Index System Including Linear Temperature Programmed Gas-Liquid Partition Chromatography. J. Chromatogr. 11, 463–471.

    Article  Google Scholar 

  24. Rakoff, H., and Rohwedder, W.K. (1992) Catalytic Deuteration of Alkynols and Their Tetrahydropyranyl Ethers, Lipids 27, 567–569.

    CAS  Google Scholar 

  25. Rohwedder, W.K. (1985) Mass Spectrometry of Lipids Labeled with Stable Isotopes, Prog. Lipid Res. 24, 1–18.

    Article  PubMed  CAS  Google Scholar 

  26. Staempfli, A.A., Blank, I., Fumeaux, R., and Fay, L.B. (1994) Study on the Decomposition of the Amadori Compound N-(1-deoxy-d-fructos-1-yl)-glycine in Model Systems: Quantification by Fast Atom Bombardment Tandem Mass Spectrometry, Biol. Mass Spectrom. 23, 642–646.

    Article  CAS  Google Scholar 

  27. Guth, H., Deterioration of Soya-bean Oil in the Presence of Light and Oxygen, Ph.D. thesis (in German). Technical University of Munich, 1991, p. 56.

  28. Guth, H., and Grosch, W. (1990) Comparison of Stored Soya-Bean and Rapeseed Oils by Aroma Extract Dilution Analysis. Lebensm. Wiss. Technol. 23, 59–65.

    CAS  Google Scholar 

  29. Gasser, U., and Grosch, W. (1990) Primary Odorants of Chicken Broth. A Comparative Study with Meat Broths from Cow and Ox, Z. Lebensm. Unters. Forsch. 190, 3–8.

    Article  CAS  Google Scholar 

  30. Schieberle, P., and Grosch, W. (1991) Potent Odorants of the Wheat Bread Crumb. Differences to the Crust and Effect of Long Dough Fermentation, Z. Lebensm. Unters. Forsch. 192, 130–135.

    Article  CAS  Google Scholar 

  31. Wagner, R., and Grosch, W. (1998) Key Odorants of French Fries, J. Am. Oil Chem. Soc. 75, 1385–1392.

    CAS  Google Scholar 

  32. Yamagata, S., Murakami, H., Terao, J., and Matsushita, S. (1983) Nonenzymatic Oxidation Products of Methyl Arachidonate, Agric. Biol. Chem. 47, 2791–2799.

    CAS  Google Scholar 

  33. Matthews, R.F., Scanlan, R.A., and Libbey, L.M. (1971) Autoxidation Products of 2,4-Decadienal, J. Am. Oil Chem. Soc. 48, 745–747.

    CAS  Google Scholar 

  34. Schieberle, P., and Grosch, W. (1981) Model Experiments About the Formation of Volatile Carbonyl Compounds, J. Am. Oil Chem. Soc. 58, 602–607.

    CAS  Google Scholar 

  35. Porter, N.A., and Wujek, D.G. (1984) Autoxidation of Polyunsaturated Fatty Acids, an Expanded Mechanistic Study. J. Am. Chem. Soc. 106, 2626–2629.

    Article  CAS  Google Scholar 

  36. Gassenmeier, K., and Schieberle, P. (1994) Formation of the Intense Flavor Compound trans-4,5-Epoxy-(E)-2-decenal in Thermally Treated Fats. J. Am. Oil Chem. Soc. 71, 1315–1319.

    CAS  Google Scholar 

  37. Meijboom, P.W., and Stroink, J.B.A. (1972) 2-trans,4-cis,7-cis-Decatrienal, the Fishy Off-flavor Occurring in Strongly Autoxidized Oils Containing Linolenic Acid or ω-3,6,9, etc., Fatty Acids, J. Am. Oil Chem. Soc. 49, 555–558.

    CAS  Google Scholar 

  38. Wilkinson, R.A., and Stark, W. (1967) A Compound Responsible for Metallic Flavor in Dairy Products. II. Theoretical Consideration of the Mechanism of Formation of Oct-1-en-3-one, J. Dairy Res., 34, 89–102.

    Article  CAS  Google Scholar 

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Author information

Author notes

  1. Jianming Lin

    Present address: Citrus Research and Education Center, University of Florida, 700 Experiment Station Rd., 33850, Lake Alfred, FL

Authors and Affiliations

  1. Nestlé Research Center, Nestec Ltd., Vers-chez-les Blanc, P.O. Box 44, CH-1000, Lausanne 26, Switzerland

    Jianming Lin, Laurent B. Fay, Dieter H. Welti & Imre Blank

Authors
  1. Jianming Lin
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  2. Laurent B. Fay
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  3. Dieter H. Welti
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  4. Imre Blank
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Correspondence to Imre Blank.

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Lin, J., Fay, L.B., Welti, D.H. et al. Quantification of key odorants formed by autoxidation of arachidonic acid using isotope dilution assay. Lipids 36, 749–756 (2001). https://doi.org/10.1007/s11745-001-0781-x

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  • DOI: https://doi.org/10.1007/s11745-001-0781-x

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