Abstract
The formation of acrylamide (AA) from L-asparagine was studied in Maillard model systems under pyrolysis conditions. While the early Maillard intermediate N-glucosylasparagine generated ∼2.4 mmol/mol AA, the Amadori compound was a less efficient precursor (0.1 mmol/mol). Reaction with α-dicarbonyls resulted in relatively low AA amounts (0.2–0.5 mmol/mol), suggesting that the Strecker aldehyde pathway is of limited relevance. Similarly, the Strecker alcohol 3-hydroxypropanamide generated low amounts of AA (0.2 mmol/mol). On the other hand, hydroxyacetone afforded more than 4 mmol/mol AA, indicating that α-hydroxycarbonyls are more efficient than α-dicarbonyls in transforming asparagine into AA. The experimental results are consistent with the reaction mechanism proposed, i.e. (i) Streckertype degradation of the Schiff base leading to azomethine ylides, followed by (ii) β-elimination of the decarboxylated Amadori compound to release AA, The functional group in β-position on both sides of the nitrogen atom is crucial. Rearrangement of the azomethine ylide to the decarboxylated Amadori compound is the key step, which is favored if the carbonyl moiety contains a hydroxyl group in β-position to the N-atom. The β-elimination step in the amino acid moiety was demonstrated by reacting under pyrolysis conditions decarboxylated model Amadori compounds obtained by synthesis.
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References
Becalski, A.; Lau, B. P.-Y.; Lewis, D.; Seaman, S., 2003, Acrylamide in food: Occurrence, sources, and modeling, J. Agric. Food Chem. 51: 802–808.
Biedermann, M.; Noti, A.; Biederman-Brem, S.; Mozzetti, V.; Grob, K., 2002, Experiments on acrylamide formation and possibilities to decrease the potential of acrylamide formation in potatoes, Mitt. Lebensm. Hyg. 93: 668–687.
Friedman, M., 2003, Chemistry, biochemistry, and safety of acrylamide. A review, J. Agric. Food Chem. 51: 4504–4526.
Gertz, C.; Klostermann, S., 2002, Analysis of acrylamide and mechanisms of its formation in deep-fried products, Eur. J. Lipid Sci. Technol. 104: 762–771.
Gilli, P.; Bertolasi, V.; Ferretti, V.; Gilli, G., 2000, Evidence for intramolecular N-H...O resonance-assisted hydrogen bonding in enaminones and related heterodienes. A combined crystal-structure, IR, NMR spectroscopic, and quantum-mechanical investigation, J. Am. Chem. Soc. 122: 10405–10417.
Granvogl, M.; Koehler, P.; Schieberle, P., 2004, An alternative pathway in the generation of acrylamide from asparagine, J. Agric. Food Chem. 52: in press.
Grigg, R.; Thianpatanagul, S., 1984, Decarboxylative transmination. Mechanism and application to the synthesis of heterocyclic compounds, J. Chem. Soc., Chem. Comm, 180–181.
Jung, M. Y.; Choi, D. S.; Ju, J. W., 2003, A novel technique for limitation of acrylamide formation in fried and baked corn chips and in French fries, J. Food Sci. 68: 1287–1290.
Keyhani, A.; Yaylayan, V. A., 1996, Pyrolysis/GC/MS analysis of N-(1-deoxy-D-fructos-lyl)-L-phenylalanine: Identification of novel pyridine and naphthalene derivatives, J. Agric. Food Chem. 44: 223–229.
Ledl F.; Schleicher E., 1990, New aspects of the Maillard reaction in foods and in the human body, Angew. Chem. Int. Ed. Engl. 29: 565–594.
Manini, P.; d’Ischia, M.; Prota, G., 2001, An unusual decarboxylative Maillard reaction between L-DOPA and D-glucose under biomimetic conditions: Factors governing competition with Pictet-Spengler condensation, J. Org. Chem. 66: 5048–5053.
Mottram, D. S.; Wedzicha, B. L.; Dodson, A. T., 2002, Food chemistry: Acrylamide is formed in the Maillard reaction, Nature 419: 448–449.
Riediker, S.; Stadler, R. H., 2003, Analysis of acrylamide in food using isotope-dilution liquid chromatography coupled with electrospray ionisation tandem mass spectrometry, J. Chromatogr. 1020: 121–130.
Rios, M. A.; Rodriguez, J., 1991, Analysis of the effect of substitution on the intramolecular hydrogen bond of malonaldehyde by ab initio calculation at the 3-21G level, Theochem. 74: 149–158.
Robert, F.; Vuataz, G.; Pollien, P.; Saucy, F.; Alonso, M.-I.; Bauwens, I., Blank, I., 2004, Acrylamide formation from asparagine under low-moisture Maillard reaction conditions. 1. Physical and chemical aspects in crystalline model systems, J. Agric. Food Chem. 52: submitted.
Rydberg, P.; Eriksson, S.; Tareke, E.; Karlsson, P.; Ehrenberg, L.; Törnqvist, M, 2003, Investigations of factors that influence the acrylamide content of heated foodstuffs, J. Agric. Food Chem. 51: 7012–7018.
Schönberg, A.; Moubacher, R., 1952, The Strecker degradation of α-amino acids, Chem. Rev. 50: 261–277
Stadler, R. H.; Robert, F.; Riediker, S.; Varga, N.; Davidek, T.; Devaud, S.; Goldmann, T.; Blank, I., 2004, In-depth mechanistic study on the formation of acrylamide and other vinylogous compounds by the Maillard reaction, J. Agric. Food Chem. 52: 5550–5558.
Stadler, R. H.; Verzegnassi, L.; Varga, N.; Grigorov, M.; Studer, A.; Riediker, S.; Schilter, B., 2003, Formation of vinylogous compounds in model Maillard reaction systems, Chem. Res. Tox. 16: 1242–1250.
Stadler, R. H.; Blank, I.; Varga, N.; Robert, F.; Hau, J.; Guy, Ph. A.; Robert, M.-C.; Riediker, S., 2002, Food chemistry: Acrylamide from Maillard reaction products, Nature 419: 449–450.
Weisshaar R.; Gutsche B., 2002, Formation of acrylamide in heated potato products-model experiments pointing to asparagine as precursor, Deutsche Lebensm. Rundsch., 98: 397–400.
Yasuhara, A.; Tanaka, Y.; Hengel, M.; Shibamoto, T., 2003, Gas chromatographic investigation of acrylamide formation in browning model systems, J. Agric. Food Chem. 51: 3999–4003.
Yaylayan, V. A., 2003, Recent advances in the chemistry of Strecker degradation and Amadori rearrangement: Implications to aroma and color formation, Food Sci. Technol. Res. 9: 1–6.
Yaylayan V. A.; Wnorowski, A., Perez Locas C., 2003, Why asparagine needs carbohydrates to generate acrylamide, J. Agric. Food Chem. 51: 1753–1757.
Zyzak, D. V.; Sanders, R. A.; Stojanovic, M.; Tallmadge, D. H; Eberhart, B. L.; Ewald, D. K.; Gruber, D. C.; Morsch, T. R.; Strothers, M. A.; Rizzi, G. P.; Villagran, M. D, 2003, Acrylamide formation mechanism in heated foods, J. Agric. Food Chem. 51: 4782–4787.
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Blank, I. et al. (2005). Mechanisms of Acrylamide Formation. In: Friedman, M., Mottram, D. (eds) Chemistry and Safety of Acrylamide in Food. Advances in Experimental Medicine and Biology, vol 561. Springer, Boston, MA. https://doi.org/10.1007/0-387-24980-X_14
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DOI: https://doi.org/10.1007/0-387-24980-X_14
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