Free radical reactions photosensitized by the human lens component, kynurenine: an EPR and spin trapping investigation.
We have undertaken electron paramagnetic resonance and spin trapping investigations of the photochemistry of kynurenine (KN), a natural component of the human eye and close analog of the principal chromophore in the young human lens 3-OH-kynurenine O-glucoside (3HKG). 5,5-Dimethyl-1-pyrroline N-oxide (DMPO) was employed as a spin trap. We found that upon UV irradiation (> 300 nm) KN photoreduces oxygen to superoxide radical (in DMSO) and nitromethane (CH3NO2) to a nitromethane radical anion (CH3NO2.-) (in air-free buffers, pH 7 and 9.5). KN also sensitized photooxidation of cysteine, NADH, EDTA, azide, and ascorbate; oxygen greatly accelerated this process. Oxidation of cysteine, NADH, and EDTA was accompanied by superoxide radical formation. Cysteinyl and azidyl radicals were detected as DMPO adducts. We also observed that KN undergoes photodegradation to a product(s) whose photosensitizing capacity is greater than that of KN itself. We postulate that: (i) 3HKG may be able to photoinitiate free radical reactions in vivo, and (ii) oxygen is an important factor determining the yields of free radical processes initiated by lenticular chromophores.
Laboratory of Molecular Biophysics, National Institute of Environmental Health Sciences, National Institute of Health, Research Triangle Park, NC, USA. REXZKA@NIEHS.NIH.GOV RESZKA@NIEHS.NIH.GOV
K J
KJ
Reszka
P
P
Bilski
C F
CF
Chignell
J
J
Dillon
D001205:Ascorbic Acid / Q000378:metabolism; D003497:Cyclic N-Oxides / Q000378:metabolism; D003545:Cysteine / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy; D004579:Electron Transport; D005123:Eye / Q000378:metabolism; D005609:Free Radicals / Q000378:metabolism; D006801:Humans; D007737:Kynurenine / Q000494:pharmacology*; D007908:Lens, Crystalline / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives / Q000378:metabolism; D008956:Models, Chemical; D015394:Molecular Structure; D009595:Nitroparaffins / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000032:analysis / Q000378:metabolism; D010777:Photochemistry; D010787:Photosensitivity Disorders / Q000378:metabolism*; D026082:Singlet Oxygen; D013053:Spectrophotometry; D013113:Spin Labels; D013482:Superoxide Dismutase / Q000378:metabolism; D013481:Superoxides / Q000378:metabolism; D014466:Ultraviolet Rays
D003497:Cyclic N-Oxides; D005609:Free Radicals; D009595:Nitroparaffins; D013113:Spin Labels; D013481:Superoxides; D026082:Singlet Oxygen; D007737:Kynurenine; C017245:5,5-dimethyl-1-pyrroline-1-oxide; D013482:Superoxide Dismutase; D003545:Cysteine; D008697:Methane; D001205:Ascorbic Acid; C008640:nitromethane; D010100:Oxygen