Formation of amines and aldehydes from parent amino acids during thermal processing of cocoa and model systems: new insights into pathways of the strecker reaction.
A method based on a derivatization with dansyl chloride and LC-MS-MS determination was developed for the quantitation of 2-methylbutyl-, 3-methylbutyl-, 2-phenylethyl-, 3-(methylthio)propyl-, and 2-methylpropylamine. Its application on unfermented, fermented, and roasted cocoas from Ghana and Sulawesi revealed an increase of all amines, except the 3-(methylthio)propylamine, during cocoa fermentation, suggesting an enzymic formation from the parent amino acids isoleucine, leucine, phenylalanine, and valine. However, a much more pronounced formation of most of the amines was measured after roasting of the cocoa, leading to concentrations in the milligrams per kilogram range. This result suggested a new "thermogenic" formation pathway of "biogenic amines". A comparison of the amounts of the amines and the aldehydes in roasted cocoa revealed similar concentrations, for example, for 2- and 3-methylbutanal and the respective amines, whereas the amounts of 2-phenylethylamine were much higher as compared to the amounts of phenylacetaldehyde. Strecker-type model systems, in which each parent amino acid was reacted with 2-oxopropanal, revealed the formation of both the amine and the aldehyde; however, in contrast to cocoa, the concentrations of the aldehydes were always much higher as compared to the amines. The results showed for the first time the thermally induced generation of "biogenic amines" from amino acids. Possible reasons for the different ratios of amines versus aldehydes formed during the roasting of cocoa or the model systems, respectively, are discussed.
Granvogl
Michael
M
Lehrstuhl für Lebensmittelchemie, Technical University of Munich, Germany.
Bugan
Susanne
S
Schieberle
Peter
P
D000447:Aldehydes / Q000032:analysis / Q000737:chemistry*; D000588:Amines / Q000032:analysis / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D002099:Cacao / Q000737:chemistry*; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005511:Food Handling / Q000379:methods*; D006358:Hot Temperature
D000447:Aldehydes; D000588:Amines; D000596:Amino Acids