A pulse radiolysis investigation of the oxidation of the melanin precursors 3,4-dihydroxyphenylalanine (dopa) and the cysteinyldopas.
The unstable quinones of 3,4-dihydroxyphenylalanine (dopa) and the most abundant cysteinyldopa isomers (2S-, 5S- and 2,5S,S'-) have been generated rapidly via disproportionation of their respective semiquinones prepared pulse radiolytically by one-electron oxidation of the corresponding dopas with azide radicals. Dopaquinone decays via a base-catalysed unimolecular cyclisation yielding leucodopachrome which, under the present conditions, is immediately oxidised by remaining dopaquinone to form dopachrome and dopa back again. Addition of cysteine increased the rate of dopaquinone decay and precluded dopachrome formation. By contrast, the cysteinyldopa quinones decayed via an acid-catalysed unimolecular cyclisation involving the cysteine side chain to form a cyclic quinone-imine observed directly for the first time. These quinone-imine intermediates subsequently rearranged to more stable phenolic benzothiazine isomers. The addition of cysteine had little effect on cysteinyldopa quinone decay and did not prevent quinone-imine formation. The absorption spectra, extinction coefficients and rate constants for formation and decay of these various transient species involved in melanisation are reported.
D003500:Cyclization; D003545:Cysteine; D003548:Cysteinyldopa / Q000031:analogs & derivatives* / Q000032:analysis; D004295:Dihydroxyphenylalanine / Q000031:analogs & derivatives*; D005609:Free Radicals; D006863:Hydrogen-Ion Concentration; D007536:Isomerism; D007700:Kinetics; D010084:Oxidation-Reduction; D010315:Particle Accelerators; D011809:Quinones
D005609:Free Radicals; D011809:Quinones; D003548:Cysteinyldopa; C034513:2-S-cysteinyldopa; C034512:2,5-S,S-dicysteinyldopa; D004295:Dihydroxyphenylalanine; D003545:Cysteine