Theaflavins (TFs) and theasinensins (TSs) are the key components formed from the enzymatic oxidation of tea catechins, contributing significantly to the biological activities and taste of black and Oolong teas. In this study, we aimed to reveal the catechin conversion and the enzymatic synthesis of TFs and TSs under reaction temperatures and pH values using polyphenol oxidase (PPO) from potato tuber (Solanum tuberosum L.). The results indicated that different temperatures, pH values and durations had significant effects on the conversion of catechins and the formation of TFs and TSs. During the reaction, the most of catechin substrates was consumed at 60–90 min after reaction initiation, and large amounts of the products TFs (0.04–0.41 mg/mL) and TSs (0.51–1.52 mg/mL) were obtained. The content of TSs was significantly higher and the maximum content of TSs was more than three times that of TFs. Reaction at a lower temperature (20 °C) is suitable for producing dimers, especially for TFs. Higher pH value resulted in higher catechin consumption and higher TSs content, while the maximum of TFs was obtained at pH 5.0. The present results provided a theoretical basis and practical guidance for the targeted processing of tea catechin dimers in vitro.
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