Elucidating dynamic behavior of synthetic supramolecular polymers in water by hydrogen/deuterium exchange mass spectrometry

Xianwen Lou, Sandra M.C. Schoenmakers, Joost L.J. van Dongen, Miguel Garcia-Iglesias, Nicolás M. Casellas, Marcos Fernández-Castaño Romera, Rint P. Sijbesma, E.W. Meijer, Anja R.A. Palmans (Corresponding author)

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A comprehensive understanding of the structure, self-assembly mechanism, and dynamics of one-dimensional supramolecular polymers in water is essential for their application as biomaterials. Although a plethora of techniques are available to study the first two properties, there is a paucity in possibilities to study dynamic exchange of monomers between supramolecular polymers in solution. We recently introduced hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize the dynamic nature of synthetic supramolecular polymers with only a minimal perturbation of the chemical structure. To further expand the application of this powerful technique some essential experimental aspects have been reaffirmed and the technique has been applied to a diverse library of assemblies. HDX-MS is widely applicable if there are exchangeable hydrogen atoms protected from direct contact with the solvent and if the monomer concentration is sufficiently high to ensure the presence of supramolecular polymers during dilution. In addition, we demonstrate that the kinetic behavior as probed by HDX-MS is influenced by the internal order within the supramolecular polymers and by the self-assembly mechanism.

Original languageEnglish
Pages (from-to)1151-1161
Number of pages11
JournalJournal of Polymer Science
Issue number12
Publication statusPublished - 15 Jun 2021

Bibliographical note

© 2021 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC.


René Lafleur and Lorenzo Albertazzi are gratefully acknowledged for initial discussions. The research in Eindhoven is supported by the Dutch Ministry of Education, Culture and Science (Gravity program 024.001.035) and the European Research Council (H2020‐EU.1.1., SYNMAT project, ID 788618). Marcos Fernández‐Castaño Romera was financially supported by the Marie Curie FP7 SASSYPOL ITN program (No. 607602). Miguel Garcia‐Iglesias acknowledges financial support from MINECO, Spain (IJCI‐2015‐252389). MINECO, Spain, Grant/Award Number: IJCI‐2015‐252389; Marie Curie FP7 SASSYPOL ITN program, Grant/Award Number: 607602; European Research Council, Grant/Award Number: 788618; Dutch Ministry of Education, Culture and Science, Grant/Award Number: 024.001.035 Funding information

FundersFunder number
Horizon 2020 Framework Programme788618
European Research CouncilH2020‐EU.1.1
Ministerie van Onderwijs, Cultuur en Wetenschap024.001.035
Ministerio de Economía y CompetitividadIJCI‐2015‐252389, 607602


    • cryoTEM
    • exchange dynamics
    • hydrogen deuterium exchange
    • self-assembly
    • supramolecular chemistry
    • supramolecular polymers


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