Spiroiminodihydantoin nucleoside formation from 2'-deoxyguanosine oxidation by [(18)O-labeled] singlet molecular oxygen in aqueous solution.
The main singlet molecular oxygen ((1)O(2)) oxidation products of free 2'-deoxyguanosine (dGuo) in aqueous solution were identified as a pair of diastereomeric spiroiminodihydantoin 2'-deoxyribonucleosides (dSp) together with 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo). In the present work, evidence is provided from (18)[(1)O(2)] and H(2) (18)O labeling experiments, using HPLC-ESI-MS/MS, that the formation of dSp is explained by the addition of water to a reactive quinonoid intermediate, and a second reaction pathway leading to dSp involves (1)O(2) oxidation of initially generated 8-oxodGuo.
Martinez
Glaucia Regina
GR
Departamento de Bioquímica e Biologia Molecular, Setor de Ciências Biológicas, Universidade Federal do Paraná, Curitiba, Brazil.
Ravanat
Jean-Luc
JL
Cadet
Jean
J
de Medeiros
Marisa Helena Gennari
MH
Di Mascio
Paolo
P
D002851:Chromatography, High Pressure Liquid; D003849:Deoxyguanosine / Q000737:chemistry*; D006151:Guanosine / Q000031:analogs & derivatives* / Q000737:chemistry; D006827:Hydantoins / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010103:Oxygen Isotopes; D026082:Singlet Oxygen; D012996:Solutions; D021241:Spectrometry, Mass, Electrospray Ionization; D013141:Spiro Compounds / Q000737:chemistry*; D053719:Tandem Mass Spectrometry; D014867:Water
D006827:Hydantoins; D010103:Oxygen Isotopes; D012996:Solutions; D013141:Spiro Compounds; C408822:spiroiminodihydantoin; D014867:Water; D006151:Guanosine; D026082:Singlet Oxygen; D003849:Deoxyguanosine