Eur. Phys. J. D 51, 89-96 (2009)
https://doi.org/10.1140/epjd/e2008-00149-4

Collision induced dissociation of deuterium enriched protonated 2^′-deoxyguanosine

Department of Chemistry, B6c, University of Liège, 6700 Liège, Belgium

Corresponding author: ^a jfgreisch@ulg.ac.be

Received: 7 January 2008
Revised: 25 May 2008
Published online: 6 August 2008

Abstract

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, [ bH₂] . The origin of the hydrogen transfer for the protonated 2'-deoxyguanosine has been investigated by collision induced dissociation of deuterium enriched molecules. [ 1'-²H] 2'-deoxyguanosine, [ 2',2''-²H₂] 2'-deoxyguanosine, and [ 5',5''-²H₂] 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.