Size Dependence of the Folding of Multiply Charged Sodium Cationized Polylactides Revealed by Ion Mobility Mass Spectrometry and Molecular Modelling

Authors

  • Dr. Julien De Winter,

    1. Mass Spectrometry Research Group, Interdisciplinary Center for Mass Spectrometry (CISMa), University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
    2. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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  • Dr. Vincent Lemaur,

    1. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory for Chemistry of Novel Materials, University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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  • Dr. Renaud Ballivian,

    1. Université de Lyon, 69622, Lyon (France)
    2. CNRS and Université de Lyon 1, UMR5579, LASIM, 69622, Villeurbanne (France)
    3. CNRS and Université de Lyon 1 UMR 5180, Sciences Analytiques, 69622, Villeurbanne (France)
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  • Dr. Fabien Chirot,

    1. Université de Lyon, 69622, Lyon (France)
    2. CNRS and Université de Lyon 1 UMR 5180, Sciences Analytiques, 69622, Villeurbanne (France)
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  • Dr. Olivier Coulembier,

    1. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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  • Dr. Rodolphe Antoine,

    1. Université de Lyon, 69622, Lyon (France)
    2. CNRS and Université de Lyon 1, UMR5579, LASIM, 69622, Villeurbanne (France)
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  • Dr. Jérôme Lemoine,

    1. Université de Lyon, 69622, Lyon (France)
    2. CNRS and Université de Lyon 1 UMR 5180, Sciences Analytiques, 69622, Villeurbanne (France)
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  • Dr. Jérôme Cornil,

    1. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory for Chemistry of Novel Materials, University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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  • Prof. Philippe Dubois,

    1. Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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  • Dr. Philippe Dugourd,

    1. Université de Lyon, 69622, Lyon (France)
    2. CNRS and Université de Lyon 1, UMR5579, LASIM, 69622, Villeurbanne (France)
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  • Dr. Pascal Gerbaux

    Corresponding author
    1. Mass Spectrometry Research Group, Interdisciplinary Center for Mass Spectrometry (CISMa), University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
    • Mass Spectrometry Research Group, Interdisciplinary Center for Mass Spectrometry (CISMa), University of Mons, UMONS, 20 Place du Parc, 7000 Mons (Belgium)
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Abstract

Ion mobility spectrometry coupled with mass spectrometry was used to experimentally determine the three-dimensional structure of multiply charged sodium cationized polylactides (PLA). In particular, the experiments were conducted to evaluate the influence of the charge state and the size on the gas-phase conformation of cationized PLA. The measured collision cross sections were then compared to calculated values obtained by computational chemistry methods. The most striking feature was the experimental and theoretical observation of a breaking point in the quasilinear relationship between the average collision cross sections and the number of monomer units for the triply charged cations. This breaking point was theoretically demonstrated, for the doubly and triply charged cations, to be associated with a significant folding of the polymer chains around the cationizing agents. The occurrence of such breaking points could be exploited to correlate the charge state of the most intense ion series observed upon electrospray ionization with the number-average molecular mass of a polymer.

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