Novel pathway for N1-acetyl-5-methoxykynuramine: UVB-induced liberation of carbon monoxide from precursor N1-acetyl-N2-formyl-5-methoxykynuramine.
Irradiation of the melatonin metabolite N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK) with UV light of 254 nm causes the release of carbon monoxide (CO) and, thus, deformylation to N(1)-acetyl-5-methoxykynuramine (AMK). Liberation of CO was demonstrated by reduction of PdCl(2) to metallic palladium, under avoidance of actions by other reductants. Photochemical AMK formation was not due to UV-induced hydroxyl radicals, because the reaction also took place with high efficiency in ethanol and 2-propanol. Moreover, AMK was generated from AFMK by UVB on a dry thin layer chromatographic plate. Although AMK seems to be the major primary product generated by UVB radiation, prolonged exposure of AFMK led to various other products, especially formed by destruction of AMK, as shown by irradiation of this latter compound. With regard to the demonstration of melatonin in skin and substantial amounts of AFMK in keratinocytes, these findings may be of dermatologic relevance.
Seever
Katinka
K
Johann Friedrich Blumenbach Institute of Zoology and Anthropology, University of Göttingen, Göttingen, Germany.
Hardeland
Rüdiger
R
D002248:Carbon Monoxide / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry; D007735:Kynuramine / Q000031:analogs & derivatives* / Q000737:chemistry; D008550:Melatonin / Q000737:chemistry; D010777:Photochemistry; D014466:Ultraviolet Rays
D017665:Hydroxyl Radical; D007735:Kynuramine; C041550:N-acetyl-N-formyl-5-methoxykynurenamine; C032131:N-acetyl-5-methoxy kynurenamine; D002248:Carbon Monoxide; D008550:Melatonin