Abstract
Supramolecular gels, which demonstrate tunable functionalities, have attracted much interest in a range of areas, including healthcare, environmental protection and energy-related technologies. Preparing these materials in a reliable manner is challenging, with an increased level of kinetic defects observed at higher self-assembly rates. Here, by combining biocatalysis and molecular self-assembly, we have shown the ability to more quickly access higher-ordered structures. By simply increasing enzyme concentration, supramolecular order expressed at molecular, nano- and micro-levels is dramatically enhanced, and, importantly, the gelator concentrations remain identical. Amphiphile molecules were prepared by attaching an aromatic moiety to a dipeptide backbone capped with a methyl ester. Their self-assembly was induced by an enzyme that hydrolysed the ester. Different enzyme concentrations altered the catalytic activity and size of the enzyme clusters, affecting their mobility. This allowed structurally diverse materials that represent local minima in the free energy landscape to be accessed based on a single gelator structure.
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Acknowledgements
The authors acknowledge the Engineering and Physical Sciences Research Council (EPSRC), Human Frontiers Science Programme (HFSP) and the Leverhulme Trust (UK) for funding. The authors also thank L. Birchall and P.F. Caponi for assistance with graphics.
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A.R.H., S.R., J.S., S.S. and R.V.U. conceived and designed the experiments. A.R.H., S.R., M.A., A.K.D., N.H., N.J. and J.B. performed the experiments. A.R.H., S.R., P.M., J.S., S.S. and R.V.U. analysed the data. S.M., J.H.v.E. and N.T.H. contributed materials/analysis tools. A.R.H., S.R., S.S. and R.V.U. co-wrote the paper.
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Hirst, A., Roy, S., Arora, M. et al. Biocatalytic induction of supramolecular order. Nature Chem 2, 1089–1094 (2010). https://doi.org/10.1038/nchem.861
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DOI: https://doi.org/10.1038/nchem.861
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