Article | Published:

Catalytic control over supramolecular gel formation

Nature Chemistry volume 5, pages 433437 (2013) | Download Citation

Abstract

Low-molecular-weight gels show great potential for application in fields ranging from the petrochemical industry to healthcare and tissue engineering. These supramolecular gels are often metastable materials, which implies that their properties are, at least partially, kinetically controlled. Here we show how the mechanical properties and structure of these materials can be controlled directly by catalytic action. We show how in situ catalysis of the formation of gelator molecules can be used to accelerate the formation of supramolecular hydrogels, which drastically enhances their resulting mechanical properties. Using acid or nucleophilic aniline catalysis, it is possible to make supramolecular hydrogels with tunable gel-strength in a matter of minutes, under ambient conditions, starting from simple soluble building blocks. By changing the rate of formation of the gelator molecules using a catalyst, the overall rate of gelation and the resulting gel morphology are affected, which provides access to metastable gel states with improved mechanical strength and appearance despite an identical gelator composition.

  • Compound C9H18N6O3

    (cis,cis)-Cyclohexane-1,3,5-tricarbohydrazide

  • Compound C17H26O7

    3,4-Bis(2-(2-methoxyethoxy)ethoxy)benzaldehyde

  • Compound C60H90N6O21

    Tris(3,4-bis(2-(2-methoxyethoxy)ethoxy)benzylidene)cyclohexane-1,3,5-tricarbohydrazide

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References

  1. 1.

    Biochemistry (W. H. Freeman, 1995).

  2. 2.

    et al. Mechanosensitive self-replication driven by self-organization. Science 327, 1502–1506 (2010).

  3. 3.

    , , , & Self-assembly of large and small molecules into hierarchically ordered sacs and membranes. Science 319, 1812–1816 (2008).

  4. 4.

    et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012).

  5. 5.

    et al. Self-reproduction of supramolecular giant vesicles combined with the amplification of encapsulated DNA. Nature Chem. 3, 775–781 (2011).

  6. 6.

    , & Autocatalytic self-replicating micelles as models for prebiotic structures. Nature 357, 57–59 (1992).

  7. 7.

    & Membrane assembly driven by a biomimetic coupling reaction. J. Am. Chem. Soc. 134, 751–753 (2012).

  8. 8.

    et al. Enzyme-assisted self-assembly under thermodynamic control. Nature Nanotech. 4, 19–24 (2009).

  9. 9.

    et al. Biocatalytic induction of supramolecular order. Nature Chem. 2, 1089–1094 (2010).

  10. 10.

    et al. β-Galactosidase-instructed formation of molecular nanofibers and a hydrogel. Nanoscale 3, 2859–2861 (2011).

  11. 11.

    et al. Enzyme-instructed self-assembly of peptide derivatives to form nanofibers and hydrogels. Biopolymers 94, 19–31 (2010).

  12. 12.

    , , & Switching of self-assembly in a peptide nanostructure with a specific enzyme. Soft Matter 7, 9665–9672 (2011).

  13. 13.

    & Biotransformation on polymer–peptide conjugates: a versatile tool to trigger microstructure formation. Angew. Chem. Int. Ed. 48, 6431–6434 (2009).

  14. 14.

    , , & Acetylcholinesterase responsive polymeric supra-amphiphiles for controlled self-assembly and disassembly. Langmuir 28, 6032–6036 (2012).

  15. 15.

    , , , & Enzymatically derived sugar-containing self-assembled organogels with nanostructured morphologies. Angew. Chem. Int. Ed. 45, 4772–4775 (2006).

  16. 16.

    et al. Enzyme promotes the hydrogelation from a hydrophobic small molecule. J. Am. Chem. Soc. 131, 11286–11287 (2009).

  17. 17.

    & Enzyme-directed assembly and manipulation of organic nanomaterials. Chem. Commun. 47, 11814–11821 (2009).

  18. 18.

    , , & van Esch, J. Two-stage enzyme mediated drug release from LMWG hydrogels. Org. Biomol. Chem. 3, 2917–2920 (2005).

  19. 19.

    , & Enzyme-triggered disassembly of dendrimer-based amphiphilic nanocontainers. J. Am. Chem. Soc. 131, 14184–14185 (2009).

  20. 20.

    , , & Silica-like malleable materials from permanent organic networks. Science 334, 965–968 (2011).

  21. 21.

    , , , & van Esch, J. H. A self-assembled delivery platform with post-production tunable release rate. J. Am. Chem. Soc. 134, 12908–12911 (2012).

  22. 22.

    et al. Synthetic homeostatic materials with chemo-mechano-chemical self-regulation. Nature 487, 214–218 (2012).

  23. 23.

    & Low molecular mass gelators of organic liquids and the properties of their gels. Chem. Rev. 97, 3133–3160 (1997).

  24. 24.

    Supramolecular gel chemistry: developments over the last decade. Chem. Commun. 47, 1379–1383 (2011).

  25. 25.

    , , & Architecture of a biocompatible supramolecular material by supersaturation-driven fabrication of its fiber network. J. Phys. Chem. B 109, 24231–24235 (2005).

  26. 26.

    , , , & Reversible optical transcription of supramolecular chirality into molecular chirality. Science 304, 278–281 (2004).

  27. 27.

    et al. Self-assembly mechanism for a naphthalene-dipeptide leading to hydrogelation. Langmuir 26, 5232–5242 (2010).

  28. 28.

    et al. Effects of hydrogen bonding and van der Waals interactions on organogelation using designed low-molecular-weight gelators and gel formation at room temperature. Langmuir 19, 8622–8624 (2003).

  29. 29.

    et al. Dissipative self-assembly of a molecular gelator by using a chemical fuel. Angew. Chem. Int. Ed. 49, 4825–4828 (2010).

  30. 30.

    et al. Tunable, high modulus hydrogels driven by ionic coacervation. Adv. Mater. 23, 2327–2331 (2011).

  31. 31.

    et al. Low-molecular-weight gelators: elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model. J. Am. Chem. Soc. 130, 9113–9121 (2008).

  32. 32.

    , , & Small molecular gelling agents to harden organic liquids: trialkyl cis-1,3,5-cyclohexanetricarboxamides. Chem. Lett. 191–192 (1997).

  33. 33.

    et al. Responsive cyclohexane-based low-molecular-weight hydrogelators with modular architecture. Angew. Chem. Int. Ed. 43, 1663–1667 (2004).

  34. 34.

    & Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation. Proc. Natl Acad. Sci. USA 102, 5938–5943 (2005).

  35. 35.

    , , , & Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties. Macromolecules 43, 1191–1194 (2010).

  36. 36.

    , , , & Modular approach to functional hyaluronic acid hydrogels using orthogonal chemical reactions. Chem. Commun. 46, 8368–8370 (2010).

  37. 37.

    et al. Dynamic combinatorial chemistry. Chem. Rev. 106, 3652–3711 (2006).

  38. 38.

    Dynamic combinatorial chemistry and virtual combinatorial libraries. Chem. Eur. J. 5, 2455–2463 (1999).

  39. 39.

    , , & Nucleophilic catalysis of hydrazone formation and transimination: implications for dynamic covalent chemistry. J. Am. Chem. Soc. 128, 15602–15603 (2006).

  40. 40.

    et al. Nucleophilic catalysis of acylhydrazone equilibration for protein-directed dynamic covalent chemistry. Nature Chem. 2, 490–497 (2010).

  41. 41.

    & Formation kinetics of fractal nanofiber networks in organogels. Appl. Phys. Lett. 79, 3518–3520 (2001).

  42. 42.

    & Mechanism of the formation of self-organized microstructures in soft functional materials. Adv. Mater. 14, 421–426 (2002).

  43. 43.

    , & Signal amplification and detection via a supramolecular allosteric catalyst. J. Am. Chem. Soc. 127, 1644–1645 (2005).

  44. 44.

    , , & Photoswitching of basicity. Angew. Chem. Int. Ed. 47, 5968–5972 (2008).

  45. 45.

    , & Activating catalysts with mechanical force. Nature Chem. 1, 133–137 (2009).

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Acknowledgements

The authors acknowledge the European Commission (a Marie Curie European Reintegration grant, R.E.) and the Netherlands Organisation for Scientific Research (a VENI grant (R.E.), a VICI grant (J.H.v.E., J.B.) and an ECHO grant (R.E., J.H.v.E., J.M.P.)) for funding.

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  1. Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

    • Job Boekhoven
    • , Jos M. Poolman
    • , Chandan Maity
    • , Feng Li
    • , Lars van der Mee
    • , Christophe B. Minkenberg
    • , Eduardo Mendes
    • , Jan H. van Esch
    •  & Rienk Eelkema

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Contributions

J.B., R.E. and J.H.v.E. designed the experiments, J.B., J.M.P., C.B.M., F.L., E.M. and R.E. performed the experiments and analysed the data, J.M.P., C.B.M., L.v.d.M., C.M. and R.E. synthesized the molecules, R.E. and J.H.v.E. guided the research and all authors contributed to discussing the results and editing the manuscript. R.E. wrote the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Jan H. van Esch or Rienk Eelkema.

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DOI

https://doi.org/10.1038/nchem.1617

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