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In-depth mechanistic study on the formation of acrylamide and other vinylogous compounds by the maillard reaction.
J Agric Food Chem. 2004 Aug 25; 52(17):5550-8.JA

Abstract

The formation of acrylamide was studied in low-moisture Maillard model systems (180 degrees C, 5 min) based on asparagine, reducing sugars, Maillard intermediates, and sugar degradation products. We show evidence that certain glycoconjugates play a major role in acrylamide formation. The N-glycosyl of asparagine generated about 2.4 mmol/mol acrylamide, compared to 0.1-0.2 mmol/mol obtained with alpha-dicarbonyls and the Amadori compound of asparagine. 3-Hydroxypropanamide, the Strecker alcohol of asparagine, generated only low amounts of acrylamide (approximately 0.23 mmol/mol), while hydroxyacetone increased the acrylamide yields to more than 4 mmol/mol, indicating that alpha-hydroxy carbonyls are much more efficient than alpha-dicarbonyls in converting asparagine into acrylamide. The experimental results are consistent with the reaction mechanism based on (i) a Strecker type degradation of the Schiff base leading to azomethine ylides, followed by (ii) a beta-elimination reaction of the decarboxylated Amadori compound to afford acrylamide. The beta-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 beta-position to the nitrogen atom. The beta-elimination step in the amino acid moiety was demonstrated by reacting under low moisture conditions decarboxylated model Amadori compounds obtained by synthesis. The corresponding vinylogous compounds were only generated if a beta-proton was available, for example, styrene from the decarboxylated Amadori compound of phenylalanine. Therefore, it is suggested that this thermal pathway may be common to other amino acids, resulting under certain conditions in their respective vinylogous reaction products.

Authors+Show Affiliations

Stadler RH
Nestlé Research Center, Vers-chez-les-Blanc, 1000 Lausanne 26, Switzerland.
Robert F
No affiliation info available
Riediker S
No affiliation info available
Varga N
No affiliation info available
Davidek T
No affiliation info available
Devaud S
No affiliation info available
Goldmann T
No affiliation info available
Hau J
No affiliation info available
Blank I
No affiliation info available

MeSH

AcetoneAcrylamideAlcoholsAsparagineChromatography, LiquidFood AnalysisGas Chromatography-Mass SpectrometryGlycosidesMagnetic Resonance SpectroscopyMaillard Reaction

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15315399

Citation

Stadler, Richard H., et al. "In-depth Mechanistic Study On the Formation of Acrylamide and Other Vinylogous Compounds By the Maillard Reaction." Journal of Agricultural and Food Chemistry, vol. 52, no. 17, 2004, pp. 5550-8.
Stadler RH, Robert F, Riediker S, et al. In-depth mechanistic study on the formation of acrylamide and other vinylogous compounds by the maillard reaction. J Agric Food Chem. 2004;52(17):5550-8.
Stadler, R. H., Robert, F., Riediker, S., Varga, N., Davidek, T., Devaud, S., Goldmann, T., Hau, J., & Blank, I. (2004). In-depth mechanistic study on the formation of acrylamide and other vinylogous compounds by the maillard reaction. Journal of Agricultural and Food Chemistry, 52(17), 5550-8.
Stadler RH, et al. In-depth Mechanistic Study On the Formation of Acrylamide and Other Vinylogous Compounds By the Maillard Reaction. J Agric Food Chem. 2004 Aug 25;52(17):5550-8. PubMed PMID: 15315399.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - In-depth mechanistic study on the formation of acrylamide and other vinylogous compounds by the maillard reaction. AU - Stadler,Richard H, AU - Robert,Fabien, AU - Riediker,Sonja, AU - Varga,Natalia, AU - Davidek,Tomas, AU - Devaud,Stéphanie, AU - Goldmann,Till, AU - Hau,Jörg, AU - Blank,Imre, PY - 2004/8/19/pubmed PY - 2004/10/8/medline PY - 2004/8/19/entrez SP - 5550 EP - 8 JF - Journal of agricultural and food chemistry JO - J Agric Food Chem VL - 52 IS - 17 N2 - The formation of acrylamide was studied in low-moisture Maillard model systems (180 degrees C, 5 min) based on asparagine, reducing sugars, Maillard intermediates, and sugar degradation products. We show evidence that certain glycoconjugates play a major role in acrylamide formation. The N-glycosyl of asparagine generated about 2.4 mmol/mol acrylamide, compared to 0.1-0.2 mmol/mol obtained with alpha-dicarbonyls and the Amadori compound of asparagine. 3-Hydroxypropanamide, the Strecker alcohol of asparagine, generated only low amounts of acrylamide (approximately 0.23 mmol/mol), while hydroxyacetone increased the acrylamide yields to more than 4 mmol/mol, indicating that alpha-hydroxy carbonyls are much more efficient than alpha-dicarbonyls in converting asparagine into acrylamide. The experimental results are consistent with the reaction mechanism based on (i) a Strecker type degradation of the Schiff base leading to azomethine ylides, followed by (ii) a beta-elimination reaction of the decarboxylated Amadori compound to afford acrylamide. The beta-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 beta-position to the nitrogen atom. The beta-elimination step in the amino acid moiety was demonstrated by reacting under low moisture conditions decarboxylated model Amadori compounds obtained by synthesis. The corresponding vinylogous compounds were only generated if a beta-proton was available, for example, styrene from the decarboxylated Amadori compound of phenylalanine. Therefore, it is suggested that this thermal pathway may be common to other amino acids, resulting under certain conditions in their respective vinylogous reaction products. SN - 0021-8561 UR - https://www.unboundmedicine.com/medline/citation/15315399/In_depth_mechanistic_study_on_the_formation_of_acrylamide_and_other_vinylogous_compounds_by_the_maillard_reaction_ DB - PRIME DP - Unbound Medicine ER -