Abstract
Numerous self-assembling molecules have been synthesized aiming at mimicking both the structural and dynamic properties found in living systems. Here we show the application of hydrogen/deuterium exchange (HDX) mass spectrometry (MS) to unravel the nanoscale organization and the structural dynamics of synthetic supramolecular polymers in water. We select benzene-1,3,5-tricarboxamide (BTA) derivatives that self-assemble in H2O to illustrate the strength of this technique for supramolecular polymers. The BTA structure has six exchangeable hydrogen atoms and we follow their exchange as a function of time after diluting the H2O solution with a 100-fold excess of D2O. The kinetic H/D exchange profiles reveal that these supramolecular polymers in water are dynamically diverse; a notion that has previously not been observed using other techniques. In addition, we report that small changes in the molecular structure can be used to control the dynamics of synthetic supramolecular polymers in water.
Highlights
Numerous self-assembling molecules have been synthesized aiming at mimicking both the structural and dynamic properties found in living systems
The formed supramolecular fibres were investigated by Forster resonance energy transfer (FRET)[33] and stochastic optical reconstruction microscopy (STORM)[34], which revealed that the dye-labelled monomers exchange from fibre-to-fibre by a release-incorporation mechanism
We show that hydrogen/deuterium exchange (HDX)-mass spectrometry (MS) is a promising technique to study the dynamics of the water-soluble supramolecular polymer based on the BTA motif, that is, the physical movements of the constituent monomers, without the use of molecular probes
Summary
Numerous self-assembling molecules have been synthesized aiming at mimicking both the structural and dynamic properties found in living systems. In order to assess the applicability of HDX-MS for supramolecular self-assembled structures in water, we selected our well-studied benzene-1,3,5-tricarboxamide (BTA) motif[31] This BTA derivative has been studied in detail with different techniques, while still many questions concerning the molecular dynamics remained unanswered[32,33,34]. The formed supramolecular fibres were investigated by Forster resonance energy transfer (FRET)[33] and stochastic optical reconstruction microscopy (STORM)[34], which revealed that the dye-labelled monomers exchange from fibre-to-fibre by a release-incorporation mechanism This monomer exchange showed half-lives in the order of hours at room temperature and appeared to occur randomly, within the 50 nanometre resolution of the STORM technique, along the entire supramolecular polymers[34]
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