Abstract
The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.
Highlights
The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood
We have recently reported that the introduction of amphiphilic side arms (C12PEG4-OH, Fig. 1a, 1) to the BTA core allows the reliable formation of thin, multiple micron length supramolecular fibres in water with a similar columnar arrangement of BTA units (Fig. 1b)[14]
We were presented with a unique situation—two similar molecules that produced similar supramolecular structures, despite measureable differences in the packing of the monomers
Summary
The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. We have recently reported that the introduction of amphiphilic side arms (C12PEG4-OH, Fig. 1a, 1) to the BTA core allows the reliable formation of thin, multiple micron length supramolecular fibres in water with a similar columnar arrangement of BTA units (Fig. 1b)[14]. Since these water-soluble BTAs have proven their utility as an aqueous supramolecular polymer and have been used to study superselectivity and spatiotemporal control of monomers[15], to elucidate the mechanisms of monomer exchange[16] and to form tailor-made hydrogels[17]. Surprised that these differences on the molecular level did not translate to the supramolecular structure, we wanted to investigate the origins and implications of this dichotomy
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