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Biocatalytic induction of supramolecular order

Nature Chemistry volume 2, pages 1089–1094 (2010)Cite this article

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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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Figure 1: Biocatalytic self-assembly and gelation.
Figure 2: Spectroscopic and structural evidence of catalytically induced supramolecular order.
Figure 3: Evidence of catalytic clusters and cooperativity.

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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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Author notes

  1. Andrew R. Hirst, Apurba K. Das & Stefano Santabarbara

    Present address: Present address: School of Physics and Astronomy, E C Stoner Building, University of Leeds, Leeds, LS2 9JT, UK (A.R.H.); Department of Chemistry, Indian Institute of Technology Indore, IET, DAVV Campus, Khandwa Road, Indore 452017, India (A.K.D.); Istituto di Biofisica, Consiglio Nazionale delle Ricerche, Via Celoria 26, 20133 Milano, Italy (S.S),

  2. Andrew R. Hirst and Sangita Roy: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Pure & Applied Chemistry, WestCHEM, University of Strathclyde, Glasgow, Scotland, UK

    Andrew R. Hirst, Sangita Roy, Meenakshi Arora, Apurba K. Das & Rein V. Ulijn

  2. Manchester Interdisciplinary Biocentre, University of Manchester, UK

    Andrew R. Hirst

  3. BioAFM Facility, Faculty of Medical and Human Sciences, The University of Manchester, Manchester, UK

    Nigel Hodson

  4. Department of EEE, University of Strathclyde, Glasgow, Scotland, UK

    Paul Murray & Stephen Marshall

  5. Department of Chemical and Process Engineering, University of Strathclyde, Glasgow, Scotland, UK

    Nadeem Javid & Jan Sefcik

  6. Delft University of Technology, Delft, Netherlands

    Job Boekhoven & Jan H. van Esch

  7. Department of Physics, University of Strathclyde, SUPA, Glasgow, Scotland, UK

    Stefano Santabarbara & Neil T. Hunt

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Contributions

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.

Corresponding author

Correspondence to Rein V. Ulijn.

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The authors declare no competing financial interests.

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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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