Oxidation of 5-hydroxy-2'-deoxyuridine into isodialuric acid, dialuric acid, and hydantoin products.
Oxidation products of cytosine, including 5-hydroxycytosine and 5-hydroxyuracil, are highly susceptible to subsequent oxidation. Here, the oxidation products of 5-hydroxy-2'-deoxyuridine have been studied by NMR and MS analyses. The initial products were diastereomers of isodialuric acid nucleoside. These products subsequently decomposed into corresponding dialuric acid derivatives at neutral pH. The position of the carbonyl and hydroxyl groups, at C5 and C6 for isodialuric acid and at C6 and C5 for dialuric acid derivatives, respectively, was determined by 1H- and 13C NMR analyses. In addition, these analyses revealed that the carbonyl groups of both isodaluric and dialuric acid derivatives exist in their fully hydrated form in aqueous solution. Finally, the dialuric acid derivatives were observed to undergo subsequent decomposition into the corresponding 5-hydroxyhydantoin derivatives. Studies of a trinucleotide containing 5-hydroxyuracil suggest that the reactions described herein for the monomer can be extrapolated to DNA.
Rivière
Johann
J
Group in the Radiation Sciences, Faculty of Medicine, University of Sherbrooke, Sherbrooke, Quebec J1H 5N4, Canada.
Bergeron
François
F
Tremblay
Sébastien
S
Gasparutto
Didier
D
Cadet
Jean
J
Wagner
J Richard
JR
D001463:Barbiturates / Q000138:chemical synthesis* / Q000737:chemistry; D003857:Deoxyuridine / Q000031:analogs & derivatives* / Q000737:chemistry*; D006827:Hydantoins / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D014498:Uracil / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry
D001463:Barbiturates; D006827:Hydantoins; C093681:isodialuric acid; C004718:dialuric acid; C074088:5-hydroxy-2'-deoxyuridine; D014498:Uracil; D003857:Deoxyuridine