Photocatalytic mechanisms of indoleamine destruction by the quinalphos metabolite 2-hydroxyquinoxaline: a study on melatonin and its precursors serotonin and N-acetylserotonin.
The redox-active quinalphos main metabolite, 2-hydroxyquinoxaline, is particularly effective under excitation by light. We have studied the photocatalytic destruction of melatonin and its precursors, because the cytoprotective indoleamine has been detected in high quantities in mammalian skin. In photooxidation reactions, in which melatonin, N-acetylserotonin and serotonin are destroyed by 2-hydroxyquinoxaline, the photocatalyst is virtually not consumed. Rates of melatonin and serotonin destruction are not changed by the singlet oxygen quencher 1,4-diazabicyclo-(2,2,2)-octane, indicating that this oxygen species is not involved in the primary reactions, so that the persistence of 2-hydroxyquinoxaline has to be explained by redox cycling. This should imply formation of an organic radical, presumably the quinoxaline-2-oxyl radical, from which 2-hydroxyquinoxaline is regenerated by electron abstraction from indolic radical scavengers. Electron donation by 2-hydroxyquinoxaline is demonstrated by reduction of the 2,2'-azino-bis-(3-ethylbenzthiazolinyl-6-sulfonic acid) cation radical under ultrasound excitation. The compound 2-hydroxyquinoxaline interacts with the specific superoxide anion scavenger Tiron. Formation of oligomeric products from melatonin and serotonin is strongly inhibited by sodium dithionite. Products from photocatalytic indolamine conversion are predominantly dimers and oligomers. No kynuramines were detected in the case of serotonin oxidation, and melatonin's otherwise prevailing oxidation product N(1)-acetyl-N(2)-formyl-5-methoxykynuramine, another cytoprotective metabolite, is only formed in relatively small quantities. The proportion between products from melatonin is changed by 1,4-diazabicyclo-(2,2,2)-octane: singlet oxygen, also formed under the influence of excited 2-hydroxyquinoxaline, only affects secondary reactions.
Behrends
Andreas
A
Institute of Zoology and Anthropology, University of Goettingen, Goettingen, Germany.
Riediger
Sonja
S
Grube
Sascha
S
Poeggeler
Burkhard
B
Haldar
Chandana
C
Hardeland
Rüdiger
R
D000975:Antioxidants / Q000737:chemistry / Q000378:metabolism; D006801:Humans; D008027:Light; D008550:Melatonin / Q000378:metabolism*; D009946:Organothiophosphorus Compounds / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry / Q000378:metabolism; D010777:Photochemistry; D011810:Quinoxalines / Q000737:chemistry*; D012701:Serotonin / Q000031:analogs & derivatives / Q000378:metabolism*
D000975:Antioxidants; D009946:Organothiophosphorus Compounds; D016877:Oxidants; D011810:Quinoxalines; C098565:2-hydroxyquinoxaline; C009145:quinalphos; D012701:Serotonin; D008550:Melatonin; C006389:N-acetylserotonin; D010100:Oxygen