Photooxidative degradation of beer bittering principles: A key step on the route to lightstruck flavor formation in beer

Isohumulones, dihydroisohumulones, tetrahydroisohumulones, and humulinones, important hop-derived bittering compounds in beer, were shown to give rise to reactive triacylmethyl radicals on interaction with triplet-excited riboflavin after spin trapping by 5,5-dimethyl-1-pyrroline N-oxide or 2-methyl-2-nitrosopropane, followed by electron paramagentic resonance spectroscopy combined with spectral simulation. Electron abstraction from the ionized beta-tricarbonyl chromophore, which is common to all five-membered ring hop derivatives, is the initial event on photoinduced degradation. Radicaloid decomposition of isohumulones leads to precursors for 3-methylbut-2-ene-1-thiol, the lightstruck constituent in beer. Interaction of reduced derivatives of isohumulones with triplet-excited riboflavin furnished radical precursors of volatile aldehydes, which may lead to the development of unpleasant stale or cardboard flavors.