Solid-state13C NMR investigations of insoluble deposits in aromatic bitters

Insoluble deposit formed in aromatic bitters produced from alcoholic extracts of about 30 different botanical materials with a dry matter content of 1.67% and 38 vol% alcohol and a characteristic astringent flavour was shown by¹³C NMR spectroscopy to be a coprecipitate of plant polyphenols, proteins and carbohydrates. The polyphenols in the deposit were flavonoids such as anthocyanidins and anthocyanins, with glucose as the principal carbohydrate and derivatives of cinnamic acid. The deposit formation in the aromatic bitters was accelerated by addition of the radical initiator 2,2′-azobis(2-amidinopropane) dihydrochloride or by addition of hydrogen peroxide in combination with iron(III) nitrate and ascorbic acid as a Fenton reagent. Polymerization of catechin and pelargonidin was shown, in model experiments, to be oxidative and to be accelerated by exposure to light. A mechanism involving oxidative polymerization of polyphenols followed by coprecipitation of polymerized polyphenols, proteins and carbohydrates is proposed for formation of deposits in alcoholic beverages of the bitters type.