在水溶液中，[（18）O标记的]单重态分子氧氧化2'-脱氧鸟苷形成螺环亚氨基二氢嘧啶核苷。

Spiroiminodihydantoin nucleoside formation from 2'-deoxyguanosine oxidation by [(18)O-labeled] singlet molecular oxygen in aqueous solution.

作者信息

Martinez Glaucia Regina, Ravanat Jean-Luc, Cadet Jean, de Medeiros Marisa Helena Gennari, Di Mascio Paolo

机构信息

Departamento de Bioquímica e Biologia Molecular, Setor de Ciências Biológicas, Universidade Federal do Paraná, Curitiba, Brazil.

出版信息

J Mass Spectrom. 2007 Oct;42(10):1326-32. doi: 10.1002/jms.1213.

DOI:10.1002/jms.1213

PMID:17902103

Abstract

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.

摘要

在水溶液中，游离2'-脱氧鸟苷（dGuo）的主要单线态分子氧（(1)O(2)）氧化产物被鉴定为一对非对映体螺环亚氨基二氢尿嘧啶2'-脱氧核糖核苷（dSp）以及8-氧代-7,8-二氢-2'-脱氧鸟苷（8-氧代dGuo）。在本研究中，利用HPLC-ESI-MS/MS进行的(18)[(1)O(2)]和H(2)(18)O标记实验提供了证据，表明dSp的形成是由于水加成到反应性醌型中间体上，并且导致dSp的第二条反应途径涉及最初生成的8-氧代dGuo的(1)O(2)氧化。