Influence of pH on the Stability of 2-Substituted 1,3-Thiazolidine-4-Carboxylic Acids in Model Solutions

Upon beer storage, the levels of staling aldehydes increase, which coincides with the appearance of characteristic off-flavors. Bound-state aldehydes have been reported as potential sources of off-flavor appearance in aging beer. This study investigated the stability of cysteinylated aldehydes, also referred to as 2-substituted 1,3-thiazolidine-4-carboxylic adds, and the release of aldehyde compounds from cysteine adducts in model solutions at different pH values that are relevant in malting and brewing. The cysteinylated aldehydes were initially synthesized for their use as reference compounds in model solutions. Confirmation of their chemical structure was obtained by H-1-NMR. The results from the stability tests showed that degradation of cysteine-bound aldehydes results in concomitant release of the free aldehydes. The rate of degradation is highly dependent on the 2-substitution pattern of the thiazolidine ring, as well as on the pH of the model solution. At malting and brewing relevant pH values (pH 4.4, 5.2, 6.0), degradation of cysteine-bound aldehydes is observed, in particular at pH 4.4, which is representative of the beer pH.