Polyfunctional Thiols in Fresh and Aged Belgian Special Beers: Fate of Hop S-Cysteine Conjugates

Abstract

Odorant polyfunctional thiols such as 4-sulfanyl-4-methylpentan-2-one, 3-sulfanylhexan-1-ol (3SHol), and 3-sulfanyl-3-methylbutan-1ol (3S3MBol) were shown to be strongly degraded in Belgian special beers after 1 year of aging. Yet, during the first 3 months, they also appeared to be synthesized in the bottle, even in the absence of yeast. Fresh filtered lager beer was spiked with nonvolatile S-cysteine conjugates of 3SHol, 3S3MBol, and 3-methylbut-2-en-1-thiol (MBT) before aging (1 to 3 months at 20°C or 5 days at 40 or 60°C). Thiol-specific para-hydroxymercuribenzoic acid extracts were analyzed by a GC-pulsed flame photometric detector, and HPLC-electrospray ionization/MS/MS was used to quantify the undegraded cysteinylated precursors. S-Cysteine conjugates were chemically degraded in the beer, releasing their corresponding thiols. The conversions were low (<1%) but could explain the trace amounts of 3SHol and 3S3MBol produced in beer during the first months of storage. On the other hand, chemical degradation of Cys-MBT in beer (although reaching up to 33%) proved not to be efficient enough to release significant amounts of the skunky off-flavor. In this case, photooxidative degradation of isohumulone most probably remains the major synthesis pathway. Complementary analyses are now needed to determine how other beer constituents, such as dicarbonyls, might participate in cysteine adduct degradation.

• Beer aging
• Cysteine-S-conjugates
• Flavor
• Polyfunctional thiols