Fast gas-phase hydrogen/deuterium exchange observed for a DNA G-quadruplex

[en] The gas-phase hydrogen/deuterium (H/D) exchange kinetics of DNA G-quadruplexes has been investigated using Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). The quadruplex [(TGGGGT)(4).3NH(4)(+)] undergoes very fast H/D exchange, in both the positive and in the negative ion modes, compared to DNA duplexes and other quadruplexes tested, and compared to the corresponding single-stranded TGGGGT. Substitution of NH4+ for K+ did not alter this fast H/D exchange, indicating that the hydrogens of the ammonium ions are not those exchanged. However, stripping of the interior cations of the quadruplex by source collision-induced dissociation (CID) in the positive ion mode showed that the presence of the inner cations is essential for the fast exchange to be possible. Molecular dynamics simulations show that the G-quadruplex is very rigid in the gas phase with NH4+ ions inside the tetrads. We suggest that the fast H/D exchange is favored by this rigid quadruplex conformation. This example illustrates that the concept that compact DNA structures exchange H for D slower than unfolded ones is a misconception. Copyright (C) 2004 John Wiley Sons, Ltd.

Research Center/Unit :

CART - Centre Interfacultaire d'Analyse des Résidus en Traces - ULiège

Disciplines :

Chemistry

Author, co-author :

Gabelica, Valérie ; Université de Liège - ULiège > Département de Chimie (Sciences) > Chimie physique, spectrométrie de masse

Rosu, Frédéric ; Université de Liège - ULiège > Département de Chimie (Sciences) > Chimie physique, spectrométrie de masse

Witt, Matthias; Bruker Daltonics Gmbh

Baykut, Gökhan; Bruker Daltonics GmbH

De Pauw, Edwin ; Université de Liège - ULiège > Département de Chimie (Sciences) > Chimie physique, spectrométrie de masse

Language :

English

Title :

Fast gas-phase hydrogen/deuterium exchange observed for a DNA G-quadruplex

Publication date :

2005

Journal title :

Rapid Communications in Mass Spectrometry

ISSN :

0951-4198

eISSN :

1097-0231

Publisher :

John Wiley & Sons, Inc, Chichester, United Kingdom

Volume :

Issue :

Pages :

201-208

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

http://www.interscience.wiley.com/

Funders :

F.R.S.-FNRS - Fonds de la Recherche Scientifique

Commentary :

Available on ORBi :

since 26 July 2008

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