[en] Collision induced dissociation in mass spectrometry of protonated nucleosides typically yields as charged fragment the protonated nucleobase augmented by one hydrogen transferred from the 2'-deoxyribose, [ bH(2)]. The origin of the hydrogen transfer for the protonated 2'-deoxyguanosine has been investigated by collision induced dissociation of deuterium enriched molecules. [ 1'-H-2] 2'-deoxyguanosine, [ 2',2aEuro(3)-H-2(2)] 2'-deoxyguanosine, and [ 5',5aEuro(3)-H-2(2)] 2'-deoxyguanosine have been studied and deuterium/hydrogen back exchange has been used following complete or partial exchange of the 2'-deoxyguanosine in solution. Based on the fragmentation of the deuterated molecular ions, the hydrogen transferred from the 2'-deoxyribose to the guanine is found to originate from the O5' atom on the 2'-deoxyribose. A fragmentation mechanism involving a hydrogen shift from the 2' position to the oxygen atom O5' and supported by the kinetic isotope effect on the survival yield curves is proposed. The influence of the 2'-deoxyguanosine conformation on the hydrogen transfer and the fragmentation mechanism is discussed.
Research Center/Unit :
Giga-Systems Biology and Chemical Biology - ULiège
Disciplines :
Chemistry
Author, co-author :
Greisch, Jean-François ; Université de Liège - ULiège > Département de chimie (sciences) > GIGA-R : Laboratoire de spectrométrie de masse (L.S.M.)
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
De Pauw, Edwin ; Université de Liège - ULiège > Département de chimie (sciences) > GIGA-R : Laboratoire de spectrométrie de masse (L.S.M.)
Language :
English
Title :
Collision induced dissociation of deuterium enriched protonated 2'-deoxyguanosine
Publication date :
January 2009
Journal title :
European Physical Journal D. Atoms, Molecules, Clusters and Optical Physics
ISSN :
1434-6060
eISSN :
1434-6079
Publisher :
Springer Science & Business Media B.V., New York, United States - New York