Hydrogen/Deuterium Exchange followed by Mass Spectrometry for Supramolecular Polymers in water

Sandra Schoenmakers s.m.c.schoenmakers@tue.nl René Lafleur Xianwen Lou Anja Palmans Bert Meijer
Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands

Hydrogen/Deuterium exchange (HDX) followed with mass spectrometry (MS) has already been used to study the structure, dynamics and folding of proteins.1 Here, we aim to apply this technique to reveal the structural dynamics of supramolecular assemblies in water2 and to investigate their copolymerization. We used supramolecular building-blocks based on benzene-1,3,5-tricarboxamides for this application, which have been shown to form supramolecular polymers in water when functionalized with a dodecyl aliphatic chain and tetra(ethylene glycol) chain at the periphery.3 A variety of techniques was used to show that monomers with an undecyl and tridecyl aliphatic chain also formed supramolecular polymers in water, while monomers with a decyl aliphatic chain formed ill-defined structures. With continuous-labeling HDX-MS the exchange dynamics, that is the physical movement of monomers between supramolecular polymers, could be studied. Experiments not only revealed that the monomer exchange increased with decreasing length of the aliphatic chain, but also that the polymers were not structurally homogeneous with some monomers more tightly bound to each other than others. The immensely fast H/D exchange of the monomers with the decyl aliphatic chains could be used to study the rate of its co-assembly with the supramolecular polymers. Pulsed-labeling HDX-MS revealed that the larger the hydrophobic mismatch between the monomers, the longer it takes to form the supramolecular copolymer. These findings emphasize the sensitivity and versatility of HDX-MS to reveal subtle differences between almost identical supramolecular polymers in water.

(1) Konermann, L.; Pan, J.; Liu, Y.H. Chem. Soc. Rev. 2011, 40 (3), 1224.

(2) Lou, X.; Lafleur, R.P.M.; Leenders, C.M.A.; Schoenmakers, S.M.C.; Matsumoto, N.M.; Baker, M.B.; van Dongen, J.L.J.; Palmans, A.R.A.; Meijer, E.W. Nat. Commun. 2017, 8 (May), 15420.

(3) Leenders, C.M.A.; Albertazzi, L.; Mes, T.; Koenigs, M.M.E.; Palmans, A.R.A.; Meijer, E.W. Chem. Commun. 2013, 49 (19), 1963.









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