[en] Gas-phase hydrogen/deuterium exchange of small oligonucleotides (dTG, dC6 and C6) with CD3OD was performed in the second hexapole of a Fourier transform ion-cyclotron resonance (FTICR) mass spectrometer. Ion activation experiments were conducted by accelerating the ions at the entrance of the H/D exchange cell under conditions promoting exclusively collisional isomerization. These experiments allowed us to assess the presence of several conformers, and to probe the height of the isomerization barrier separating these conformers. Ion mobility experiments were also performed. Their results were consistent with the H/D exchange data. A model accounting for the competing isomerization and H/D exchange reactions is proposed. Comparing the ion acceleration experiments for H/D exchange and for ion mobility reveals that the most compact conformer displays the fastest H/D exchange. This observation shows that H/D exchange and ion mobility provide us with complementary information because hydrogen accessibility and macromolecule compactness are not univocally associated.
Research Center/Unit :
CART - Centre Interfacultaire d'Analyse des Résidus en Traces - ULiège
Disciplines :
Chemistry
Author, co-author :
Balbeur, Dorothée ; Université de Liège - ULiège > Département de chimie (sciences) > GIGA-R : Laboratoire de spectrométrie de masse (L.S.M.)
Widart, Joëlle ; Université de Liège - ULiège > Département de pharmacie > Département de pharmacie
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Cravello, Laetitia; Waters Corporation, Manchester, United Kingdom
De Pauw, Edwin ; Université de Liège - ULiège > Département de chimie (sciences) > GIGA-R : Laboratoire de spectrométrie de masse (L.S.M.)
Language :
English
Title :
Detection of Oligonucleotide Gas-Phase Conformers: H/D Exchange and Ion Mobility as Complementary Techniques
Publication date :
08 April 2008
Journal title :
Journal of the American Society for Mass Spectrometry
ISSN :
1044-0305
eISSN :
1879-1123
Publisher :
Elsevier Science, New York, United States - New York
Volume :
19
Issue :
7
Pages :
938-946
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
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