[en] The combination between ion mobility mass spectrometry and molecular dynamics simulations is demonstrated for the first time to afford valuable information on structural changes undergone by dendriplexes containing ds-DNA and low-generation dendrimers when transferred from the solution to the gas phase. Dendriplex ions presenting 1:1 and 2:1 stoichiometries are identified using mass spectrometry experiments, and the collision cross sections (CCS) of the 1:1 ions are measured using drift time ion mobility experiments. Structural predictions using Molecular Dynamics (MD) simulations showed that gas-phase relevant structures, i.e., with a good match between the experimental and theoretical CCS, are generated when the global electrospray process is simulated, including the solvent molecule evaporation, rather than abruptly transferring the ions from the solution to the gas phase. The progressive migration of ammonium groups (either NH4+ from the buffer or protonated amines of the dendrimer) into the minor and major grooves of DNA all along the evaporation processes is shown to compact the DNA structure by electrostatic and hydrogen-bond interactions. The subsequent proton transfer from the ammonium (NH4+ or protonated amino groups) to the DNA phosphate groups allows creation of protonated phosphate/phosphate hydrogen bonds within the compact structures. MD simulations showed major structural differences between the dendriplexes in solution and in the gas phase, not only due to the loss of the solvent but also due to the proton transfers and the huge difference between the solution and gas-phase charge states.
Research center :
CIRMAP - Centre d'Innovation et de Recherche en Matériaux Polymères
Disciplines :
Chemistry
Author, co-author :
Saintmont, Fabrice ; Organic Synthesis & Mass Spectrometry Laboratory, Interdisciplinary Center for Mass Spectrometry (CISMa), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium ; Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, Research Institute for Science and Engineering of Materials, University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium
Hoyas, Sébastien ; Organic Synthesis & Mass Spectrometry Laboratory, Interdisciplinary Center for Mass Spectrometry (CISMa), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium ; Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, Research Institute for Science and Engineering of Materials, University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium
Rosu, Frédéric ; Univ. Bordeaux, CNRS, INSERM, Institut Européen de Chimie et Biologie (IECB, UAR3033, US001), 2 rue Robert Escarpait, 33607 Pessac, France
Gabélica, Valérie ; Univ. Bordeaux, CNRS, INSERM, Institut Européen de Chimie et Biologie (IECB, UAR3033, US001), 2 rue Robert Escarpait, 33607 Pessac, France ; Univ. Bordeaux, INSERM, CNRS, Acides Nucléiques Régulations Naturelle et Artificielle (ARNA, U1212, UMR5320), IECB, 2 rue Robert Escarpit, 33607 Pessac, France
Brocorens, Patrick ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Gerbaux, Pascal ; Université de Mons - UMONS > Faculté des Sciences > Service de Synthèse et spectrométrie de masse organiques
Language :
English
Title :
Structural Characterization of Dendriplexes In Vacuo: A Joint Ion Mobility/Molecular Dynamics Investigation.
Publication date :
03 August 2022
Journal title :
Journal of the American Society for Mass Spectrometry
S836 - Synthèse et spectrométrie de masse organiques
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Funders :
Fonds De La Recherche Scientifique - FNRS
Funding text :
The drift tube IMS experiments were carried out at the Plateforme de BioPhysicochimie Structurale of the IECB. F.S. and S.H. thank the University of Mons and the “Fonds pour la Recherche Industrielle et Agricole” for their Ph.D. grants. The work in the Laboratory for Chemistry of Novel Materials was supported by the “Consortium des Equipements de Calcul Intensif” funded by the Fonds National de la Recherche Scientifique (F.R.S.-FNRS) under Grant No. 2.5020.11.
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