Structural insight into polyphenol oxidation during black tea fermentation

Polyphenol oxidation during fermentation plays a critical role in the formation of flavor and function of black tea. However, how the specific structures of tea polyphenols affect their oxidation kinetics during black tea fermentation is still unknown. Here, we found that the oxidations of tea polyphenols, including 7 catechins, 4 phenolic acids and 11 flavonoid glycosides followed pseudo-first-order kinetics during fermentation. Molecular structure and oxygen concentration collaboratively regulated the oxidation rate of different polyphenols. Pyrogallol structure was more easily to be oxidized than catechol and monophenol structure in B-ring, the gallic group in C-ring could inhibit oxidation of catechins, while the role of sugar moiety of flavonoid glycosides was differentiating. In addition, oxygen was found to be the key factor limiting the oxidation rate of polyphenols in regular black tea fermentation, and the oxidation rate constants of tea polyphenols were linearly and positively correlated with oxygen concentration.