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Spiroiminodihydantoin nucleoside formation from 2′‐deoxyguanosine oxidation by [ 18 O‐labeled] singlet molecular oxygen in aqueous solution
Author(s) -
Martinez Glaucia Regina,
Ravanat JeanLuc,
Cadet Jean,
de Medeiros Marisa Helena Gennari,
Di Mascio Paolo
Publication year - 2007
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1213
Subject(s) - chemistry , singlet oxygen , deoxyguanosine , aqueous solution , deoxyribonucleosides , photochemistry , singlet state , nucleoside , diastereomer , medicinal chemistry , oxygen , stereochemistry , organic chemistry , adduct , nuclear physics , physics , excited state , enzyme
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. Copyright © 2007 John Wiley & Sons, Ltd.