Unusual Profile of Thiol Precursors in Special Malts: First Evidence of Chemical Glutathione-/γGluCys- and CysGly-/Cys- Conversions

Abstract

Polyfunctional thiols (PFTs) present in beers or in wines are known to be released by yeast, during fermentation, from bound forms originally found in raw materials. In the brewing field, huge amounts of S-conjugates have been evidenced in several dual-purpose hop varieties. Malt, however, being the major raw material of beer, could also be a significant contributor of PFTs to beer (cysteinylated, Cys- and glutathionylated, G- precursors of 3SHol already identified in a few samples of barley and malt). Forty-two barley malts from 2 to 1500 EBC and five other malted cereals were screened to characterize their thiol precursor profile (G- and Cys- as well as dipeptidic bound CysGly- and γGluCys- forms of 3SHol). First, it was confirmed that G-3SHol was ubiquitous reaching up to 320 µg/kg in some samples, whereas Cys-3SHol remained at a trace level of up to 13 µg/ kg. Moreover, for the first time, dipeptidic bound forms of 3SHol were evidenced in malt (up to 10 and 11 µg/kg for CysGly-3SHol and γGluCys-3SHol, respectively). In pale malts, the level of the CysGly- form was shown to be proportional to that of G-3SHol (in situ γGT during the malting process). This appeared to be no longer true for special malts (ranging from 5 to 45°EBC), whose CysGly-3SHol level correlated instead with Cys-3SHol (suspected chemical conversion from the dipeptide conjugate). As for γGluCys-3SHol, it was only found in the special barley malts (indicating another chemical break of the Cys-Gly bond, here on G-3SHol) and in malted rye, spelt, and wheat. No precursors were found in roasted malt.