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Structure and Dynamics of Supramolecular Polymers: Wait and See.

ABSTRACT: The introduction of stereogenic centers in supramolecular building blocks is used to unveil subtle changes in supramolecular structure and dynamics over time. Three stereogenic centers based on deuterium atoms were introduced in the side chains of a benzene-1,3,5-tricarboxamide (BTA) resulting in a supramolecular polymer in water that at first glance has a structure and dynamics identical to its achiral counterpart. Using three different techniques, the properties of the double helical polymers are compared after 1 day and 4 weeks. An increase in helical preference is observed over time as well as a decrease in the helical pitch and monomer exchange dynamics. It is proposed that the polymer of the chiral monomer needs time to arrive at its maximal preference in helical bias. These results indicate that the order and tight packing increase over time, while the dynamics of this supramolecular polymer decrease over time, an effect that is typically overlooked but unveiled by the isotopic chirality.

SUBMITTER: Schoenmakers SMC

PROVIDER: S-EPMC9118549 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Structure and Dynamics of Supramolecular Polymers: Wait and See.

Schoenmakers Sandra M C SMC Spiering A J H AJH Herziger Svenja S Böttcher Christoph C Haag Rainer R Palmans Anja R A ARA Meijer E W EW

ACS macro letters 20220509 5

The introduction of stereogenic centers in supramolecular building blocks is used to unveil subtle changes in supramolecular structure and dynamics over time. Three stereogenic centers based on deuterium atoms were introduced in the side chains of a benzene-1,3,5-tricarboxamide (BTA) resulting in a supramolecular polymer in water that at first glance has a structure and dynamics identical to its achiral counterpart. Using three different techniques, the properties of the double helical polymers ...[more]

PMID: 35570802

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Project description:Polar cosolvents are commonly used to guide the self-assembly of amphiphiles in water. Here we investigate the influence of the cosolvent acetonitrile (ACN) on the structure and dynamics of a supramolecular polymer in water, which is based on the well-known benzene-1,3,5-tricarboxamide motif. Hydrogen/deuterium exchange mass spectroscopy measurements show that a gradual increase in the amount of ACN results in a gradual increase in the exchange dynamics of the monomers. In contrast, the morphology of the supramolecular polymers remains unchanged up to 15% of ACN, but then an abrupt change occurs and spherical aggregates are formed. Remarkably, this abrupt change coincides with the formation of micro-heterogeneity in the water-ACN mixtures. The results illustrate that in order to completely characterize supramolecular polymers it is important to add time-resolved measurements that probe their dynamic behavior, to the conventional techniques that are used to assess the morphology of the polymers. Subsequently we have used time-resolved measurements to investigate the influence of the concentration of ACN on the polymerization and depolymerization rates of the supramolecular polymers. Polymerization occurs within minutes when molecularly dissolved monomers are injected from ACN into water and is independent of the fraction of ACN up to 15%. In the depolymerization experiments-initiated by mixing equilibrated supramolecular polymers with dissolved monomers-the equilibration of the system takes multiple hours and does depend on the fraction of ACN. Interestingly, the longest equilibration time of the polymers is observed at a critical solvent composition of around 15% ACN. The differences in the timescales detected in the polymerization and depolymerization experiments are likely correlated to the non-covalent interactions involved, namely the hydrophobic effect and hydrogen-bonding interactions. We attribute the observed fast kinetics in the polymerization reactions to the hydrophobic effect, whereas the formation of intermolecular hydrogen bonds is the retarding factor in the equilibration of the polymers in the depolymerization experiments. Molecular dynamics simulations show that the latter is a likely explanation because ACN interferes with the hydrogen bonds and loosens the internal structure of the polymers. Our results highlight the importance of the solution conditions during the non-covalent synthesis of supramolecular polymers, as well as after equilibration of the polymers.

Dataset Information

Structure and Dynamics of Supramolecular Polymers: Wait and See.

Publications

Structure and Dynamics of Supramolecular Polymers: Wait and See.

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