A pulse radiolysis investigation of the oxidation of indolic melanin precursors: evidence for indolequinones and subsequent intermediates.
The rate constants associated with the series of successive transient absorptions initiated by one-electron oxidation of 5,6-dihydroxyindole (DHI), 5,6-dihydroxyindole-2-carboxylic acid (DHICA), precursors of melanin, and N-methyl-5,6-dihydroxyindole (NMDHI), a model compound, have been studied by pulse radiolysis. The initial transient species resulting from N3. oxidation reaction at pH 7.3-7.4 are assigned as the corresponding semiquinones. In each case, these radicals decayed, probably by disproportionation, into products most readily monitored in the 400-430 nm region. For DHI, the decay in this region could be fitted by two parent concentration independent first-order processes. These may correspond to transformations between 5,6-indolequinone, and its quinone-imine and quinone-methide tautomers. With NMDHI, on the other hand, a single longer-lived product with a peak around 430 nm predominated after decay of the corresponding radical, due almost certainly to N-methyl-5,6-indolequinone. The data appear to exclude significant melanin polymerisation by condensation of semiquinones, reaction of semiquinones with dihydroxyindoles, self-addition of indolequinones or tautomers, or reaction of indolequinones or tautomers with the parent dihydroxyindoles. It is suggested that polymerisation of melanin may rather occur by stepwise addition of indolequinone methide/imine to reduced oligomeric species.
Lambert
C
C
Paterson Institute for Cancer Research, Christie Hospital and Holt Radium Institute, Manchester, UK.
Chacon
J N
JN
Chedekel
M R
MR
Land
E J
EJ
Riley
P A
PA
Thompson
A
A
Truscott
T G
TG
D007211:Indoles; D007700:Kinetics; D008543:Melanins; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011809:Quinones; D013053:Spectrophotometry; D013329:Structure-Activity Relationship; D013861:Thiocyanates
D007211:Indoles; D008543:Melanins; D011809:Quinones; D013861:Thiocyanates; C030692:5,6-dihydroxy-2-indolylcarboxylic acid; C061554:N-methyl-5,6-dihydroxyindole; C009941:potassium thiocyanate; C033871:5,6-dihydroxyindole