The kinetics of β-elimination of cystine and the formation of lanthionine in gliadin.
When gliadin, a mixture of wheat storage proteins containing only intramolecular disulfide (SS) bonds, is heated at high temperatures and preferably at alkaline pH, the SS bonds are cleaved by β-elimination reactions leading to decreased cystine levels and the generation of dehydroalanine (DHA) and free sulfhydryl (SH) groups. DHA and the free SH group of cysteine can further react to form the irreversible cross-link lanthionine (LAN). The kinetics of this reaction were studied by heating model systems containing gliadin at different pH values (pH 6.0, 8.0 and 11.0) at temperatures up to 120 °C. Multiresponse modeling was applied to simultaneously describe the course of the reaction partners, intermediates and products. The estimated kinetic parameters indicate that the reaction rate constant for the elimination reaction increases with temperature and pH. Moreover, the predominant reaction consuming the intermediary DHA is the cross-link with cysteine to form LAN following second-order reaction kinetics. The corresponding reaction rate constant is less dependent on temperature and pH. Use of the proposed kinetic model to estimate reaction product concentrations in cereal-based foods allowed us to conclude that the β-elimination reaction may be less important during, e.g., bread making, but may well contribute to gluten network formation during the production of soft wheat products. It may also well be relevant in the production of bioplastics made from gluten.
Lagrain
Bert
B
Centre for Food and Microbial Technology and Leuven Food Science and Nutrition Research Centre, Katholieke Universiteit Leuven, Kasteelpark Arenberg 20, B-3001 Leuven, Belgium. bert.lagrain@biw.kuleuven.be
De Vleeschouwer
Kristel
K
Rombouts
Ine
I
Brijs
Kristof
K
Hendrickx
Marc E
ME
Delcour
Jan A
JA
D000409:Alanine / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D003553:Cystine / Q000737:chemistry*; D004220:Disulfides / Q000737:chemistry; D005903:Gliadin / Q000737:chemistry*; D006358:Hot Temperature; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D013440:Sulfides / Q000138:chemical synthesis*
D004220:Disulfides; D013440:Sulfides; D003553:Cystine; D005903:Gliadin; C001520:lanthionine; D000409:Alanine