title: Model sclerotization studies. 4. Generation of N-acetylmethionyl catechol adducts during tyrosinase-catalyzed oxidation of catechols in the presence of N-acetylmethionine.
abstract: Incubation of catechol with mushroom tyrosinase in the presence of N-acetylmethionine resulted in the generation of an adduct. This product was identified to be N-acetylmethionyl catechol, on the basis of spectral characteristics and well-characterized chemical reaction of o-benzoquinone with N-acetylmethionine. Enzyme-catalyzed oxidation of catechol and the subsequent nonenzymatic addition of the resultant quinone to N-acetylmethionine accounted for the observed reaction. That the reaction is not confined to catechol alone, but is of general occurrence, can be demonstrated by the facile generation of similar adducts in incubation mixtures containing N-acetylmethionine, tyrosinase, and different N-acetylmethionines, such as 4-methylcatechol and N-acetyldopamine. Attempts to duplicate the reaction with insect cuticular phenoloxidases were not successful, as the excess N-acetylmethionine used in the reaction inhibited their activity. Nevertheless, occurrence of this nonenzymatic reactivity. Nevertheless, occurrence of this nonenzymatic reaction between N-acetylmethionine and mushroom tyrosinase-generated quinones indicates that a similar reaction between enzymatically generated quinones in the cuticle with protein-bound methionine moiety is likely to occur during in vivo quinone tanning as well.
authors.affiliation: Department of Biology, University of Massachusetts at Boston 02125, USA. sugumaran@umbsky.cc.umb.edu
authors.forename: M
authors.initials: M
authors.lastname: Sugumaran
authors.forename: E
authors.initials: E
authors.lastname: Nelson
mesh_terms: D000818:Animals; D001487:Basidiomycota / Q000201:enzymology; D002396:Catechols / Q000737:chemistry* / Q000378:metabolism; D002850:Chromatography, Gel; D002851:Chromatography, High Pressure Liquid; D004175:Diptera / Q000201:enzymology; D004298:Dopamine / Q000031:analogs & derivatives / Q000737:chemistry; D018402:Manduca / Q000201:enzymology; D008715:Methionine / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism; D014442:Monophenol Monooxygenase / Q000302:isolation & purification / Q000378:metabolism*; D018696:Neuroprotective Agents / Q000737:chemistry; D010084:Oxidation-Reduction; D011809:Quinones / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D002396:Catechols; D018696:Neuroprotective Agents; D011809:Quinones; C018599:4-methylcatechol; C006374:N-acetyldopamine; C006379:N-acetylmethionine; D008715:Methionine; D014442:Monophenol Monooxygenase; D004298:Dopamine