Mechanism of activation of 1,2-dehydro-N-acetyldopamine for cuticular sclerotization.
The mechanism of oxidation of 1,2-dehydro-N-acetyldopamine (dehydro NADA) was examined to resolve the controversy between our group and Andersen's group regarding the reactive species involved in beta-sclerotization. While Andersen has indicated that dehydro NADA quinone is the beta-sclerotizing agent [Andersen, 1989], we have proposed quinone methides as the reactive species for this process [Sugumaran, 1987; Sugumaran, 1988]. Since dehydro NADA quinone has not been isolated or identified till to date, we studied the enzymatic oxidation of dehydro NADA in the presence of quinone traps to characterize this intermediate. Accordingly, both N-acetylcysteine and o-phenylenediamine readily trapped the transiently formed dehydro NADA quinone as quinone adducts. Interestingly, when the enzymatic oxidation was performed in the presence of o-aminophenol or different catechols, adduct formation between the dehydro NADA side chain and the additives had occurred. The structure of the adducts is in conformity with the generation and reactions of dehydro NADA quinone methide (or its radical). This, coupled with the fact that 4-hydroxyl or amino-substituted quinones instantly transformed into p-quinonoid structure, indicates that dehydro NADA quinone is only a transient intermediate and that it is the dehydro NADA quinone methide that is the thermodynamically stable product. However, since this compound is chemically more reactive due to the presence of both quinone methide and acylimine structure on it, the two side chain carbon atoms are "activated." Based on these considerations, it is suggested that the quinone methide derived from dehydro NADA is the reactive species responsible for cross-link formation between dehydro NADA and cuticular components during beta-sclerotization.
Sugumaran
M
M
Department of Biology, University of Massachusetts, Boston 02125.
Schinkmann
K
K
Dali
H
H
D000627:Aminophenols / Q000378:metabolism; D000818:Animals; D002396:Catechols / Q000378:metabolism; D003543:Cysteamine / Q000378:metabolism; D004298:Dopamine / Q000031:analogs & derivatives* / Q000378:metabolism; D007313:Insecta / Q000378:metabolism*; D010084:Oxidation-Reduction; D010655:Phenylenediamines / Q000378:metabolism; D013053:Spectrophotometry; D013056:Spectrophotometry, Ultraviolet
D000627:Aminophenols; D002396:Catechols; D010655:Phenylenediamines; C027667:2-aminophenol; C006374:N-acetyldopamine; D003543:Cysteamine; C053357:1,2-dehydro-N-acetyldopamine; C034193:1,2-diaminobenzene; C034221:catechol; D004298:Dopamine