The hydroxylation of tryptophan.
Products of the chemical hydroxylation of tryptophan by Fenton and Udenfriend reactions are similar to those obtained by ionizing radiation. When tryptophan is exposed to either of these systems, a mixture of four hydroxytryptophans, oxindole-3-alanine, and N-formylkynurenine is formed. This observation indicates that the hydroxyl radical attacks the aromatic nucleus as well as the 2 and 3 positions of the pyrrole ring. During gamma-radiolysis of nitrous oxide-saturated tryptophan solution and in the absence of oxygen or ferric edta, the hydroxyl radical adduct (or hydroxycyclohexadienyl radical) of tryptophan undergoes dimerization and polymerization, which results in a yellow product with maximal absorbance at 425 nm. In the presence of ferric edta, or in a Fenton system, the hydroxyl radical adduct disproportionates, and hydroxylated derivatives are formed. The yields of the hydroxytryptophans are proportional to the concentration of ferric edta to a limiting yield of 54% of the theoretical yield, which is taken to be one hydroxylated product per two hydroxyl radicals. Under these conditions, 4-, 5-, 6-, and 7-hydroxy-derivatives of tryptophan are found in the proportion 4:2:2:3, respectively. The presence of dioxygen during gamma-radiolysis increases the yield of N-formylkynurenine, but does not affect the total yield of hydroxytryptophans. Similarly, tryptophan subjected to the Udenfriend reaction yields 4-, 5-, 6-, and 7-hydroxytryptophan and N-formylkynurenine in approximately equal amounts.
Maskos
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Biodynamics Institute, Louisiana State University, Baton Rouge 70803-1800.
Rush
J D
JD
Koppenol
W H
WH
D001205:Ascorbic Acid; D002851:Chromatography, High Pressure Liquid; D004492:Edetic Acid / Q000494:pharmacology; D005290:Ferric Compounds / Q000494:pharmacology; D005720:Gamma Rays; D006861:Hydrogen Peroxide; D006863:Hydrogen-Ion Concentration; D006878:Hydroxides / Q000378:metabolism; D017665:Hydroxyl Radical; D006900:Hydroxylation; D007501:Iron; D007737:Kynurenine / Q000031:analogs & derivatives / Q000378:metabolism; D046911:Macromolecular Substances; D009609:Nitrous Oxide; D010100:Oxygen; D010777:Photochemistry; D011675:Pulse Radiolysis; D013053:Spectrophotometry; D014364:Tryptophan / Q000378:metabolism*
C045076:Fenton's reagent; D005290:Ferric Compounds; D006878:Hydroxides; D046911:Macromolecular Substances; C007772:N'-formylkynurenine; D017665:Hydroxyl Radical; D007737:Kynurenine; D014364:Tryptophan; D004492:Edetic Acid; D006861:Hydrogen Peroxide; D007501:Iron; D009609:Nitrous Oxide; C019179:Fe(III)-EDTA; D001205:Ascorbic Acid; D010100:Oxygen