It has been reported earlier that when macerated tea leaf is fermented at lower pH, the resultant black tea contains increased levels of theaflavin, an important quality marker in black tea. In an attempt to investigate the biochemistry and chemistry underlying this observation, in vitro oxidation experiments using polyphenol oxidase (PPO) from fresh tea leaves, horseradish peroxidase (POD), and tea catechins, precursors for theaflavins, were carried out. In vitro oxidation experiments using crude tea PPO resulted in higher content of theaflavins at pH 4.5 in comparison with pH 5.5, the normal pH of the macerated tea leaf. When purified PPO was used in the in vitro system, surprisingly a reversal of this trend was observed, with more theaflavins being formed at the higher pH. A combination of pure tea PPO and POD led to an observation similar to that with the crude enzyme preparation, suggesting a possible role for POD in the formation or degradation of theaflavin. POD was observed to oxidize theaflavins in the presence of H(2)O(2), leading to the formation of thearubigin, another black tea pigment. This paper demonstrates that tea PPO, while oxidizing catechins, generates H(2)O(2). The amount of H(2)O(2) produced is greater at pH 5.5, the optimum pH for PPO activity, than at pH 4.5. Hence, an observed increase of theaflavins in black teas fermented at pH 4.5 appears to be due to lower turnover of formed theaflavins into thearubigins.

l-Oxido-l,2-benziodoxol-3(1 H)-one (o-iodosyl benzoate) shows a significant a-effect in the cleavage of p-nitrophenyl acetate; however, unusual solvent effects are absent in dimethyl sulphoxide-water solvent mixtures.

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Covesicles of 10 mol % Ci8 (la), Cig (lb), or C2o (lc) p-nitrophenyl benzoate functional surfactants with 90 mol % Ci6, Ci8, or C2o nonfunctional surfactants (2a-c), prepared at pH 3.8, could be surface differentiated by esterolytic cleavage of the exovesicular benzoate head groups with glutathione in pH 8 Tris buffer. Flip-flop equilibration of intact endovesicular p-nitrophenyl benzoate surfactant molecules between exo-and endovesicular loci could then be followed. The kinetics of the exovesicular and endovesicular benzoate esterolyses and the dynamics of the flip-flop equilibrations are examined as functions of surfactant chain length and covesicle composition.

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