Open AccessFragmentation of deprotonated ions of oligodeoxynucleotides carrying a 5-formyluracil or 2-aminoimidazolone
Author(s) -
Yinsheng Wang,
Lijie Men,
Vivekananda Shetty
Publication year - 2002
Publication title -
journal of the american society for mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.961
H-Index - 127
eISSN - 1879-1123
pISSN - 1044-0305
DOI - 10.1016/s1044-0305(02)00452-x
Subject(s) - chemistry , thymine , cleavage (geology) , fragmentation (computing) , deprotonation , guanine , tandem mass spectrometry , stereochemistry , dissociation (chemistry) , thymidine , ion , dna , deoxyuridine , bond cleavage , mass spectrometry , nucleotide , biochemistry , chromatography , organic chemistry , geotechnical engineering , fracture (geology) , computer science , engineering , catalysis , gene , operating system
2-Aminoimidazolone and 5-formyluracil are major one-electron photooxidation products of guanine and thymine in oligodeoxynucleotides (ODNs). Herein we report the HPLC isolation and tandem mass spectrometric characterization of ODNs carrying those types of base modifications. Collision-activated dissociation (CAD) of the deprotonated ODN ions leads to cleavages of the 3' C-O bond adjacent to the modification site, which provides enough information for locating the sites of modification. The cleavage 3' to 5-formyl-2'-deoxyuridine is in contrast to the observation that there is no cleavage 3' to an unmodified thymidine under similar conditions. In addition we observed that at high charge states, the loss of 5-formyluracil as an anion and the resulting strand cleavage is predominant over cleavages at other sites.