Oxidation of 6-hydroxydopamine catalyzed by tyrosinase

1. The oxidation of 3,4-dihydroxyphenylethylamine (dopamine) by O2 catalyzed by tyrosinase yields 4-(2-aminoethyl)-1,2-benzoquinone, with its amino group protonated (o-dopaminequinone-H+), which evolves non-enzymatically through two branches or sequences of reactions, whose respective operations are determined by the pH of the medium. 2. The cyclization branch of o-dopaminequinone-H+ takes place in the entire range of pH and is the only significant branch at pH > or = 6. 3. The hydroxylation branch of o-dopaminequinone-H+ only operates significantly at pH < 6, and involves the accumulation of 2,4,5-trihydroxyphenylethylamine (6-hydroxydopamine), identified by high performance liquid chromatography (HPLC). 4. 6-hydroxydopamine is also a substrate of tyrosinase. The identification and evolution of the oxidation products of 6-hydroxydopamine has been carried out by spectrophotometry and HPLC assays.