Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder

Abstract

With the world’s focus on reducing our dependency on fossil-fuel energy, the scientific community can investigate new plastic materials that are much less dependent on petroleum than are conventional plastics. Given increasing environmental issues, the idea of replacing plastics with water-based gels, so-called hydrogels, seems reasonable. Here we report that water and clay (2–3 per cent by mass), when mixed with a very small proportion (<0.4 per cent by mass) of organic components, quickly form a transparent hydrogel. This material can be moulded into shape-persistent, free-standing objects owing to its exceptionally great mechanical strength, and rapidly and completely self-heals when damaged. Furthermore, it preserves biologically active proteins for catalysis. So far1 no other hydrogels, including conventional ones formed by mixing polymeric cations and anions2,3 or polysaccharides and borax4, have been reported to possess all these features. Notably, this material is formed only by non-covalent forces resulting from the specific design of a telechelic dendritic macromolecule with multiple adhesive termini for binding to clay.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Schematic structures of dendritic G n -binders ( n = 1–3) and a monodendron analogue of G3-binder (PEG-G3-dendron).
Figure 2: Non-covalent preparation of hydrogels.
Figure 3: Rheological properties (20 °C) of hydrogels.
Figure 4: Shape-persistent, free-standing macroscopic objects moulded from a hydrogel.
Figure 5: Catalytic activities of myoglobin in hydrogels.

References

  1. Hirst, A. R., Escuder, B., Miravet, J. F. & Smith, D. K. High-tech applications of self-assembling supramolecular nanostructured gel-phase materials: from regenerative medicine to electronic devices. Angew. Chem. Int. Edn 47, 8002–8018 (2008)

    Article  CAS  Google Scholar 

  2. Marsich, E. et al. Alginate/lactose-modified chitosan hydrogels: a bioactive biomaterial for chondrocyte encapsulation. J. Biomed. Mater. Res. A 84A, 364–376 (2007)

    Article  Google Scholar 

  3. Crompton, K. E. et al. Polylysine-functionalised thermoresponsive chitosan hydrogel for neural tissue engineering. Biomaterials 28, 441–449 (2007)

    Article  CAS  Google Scholar 

  4. Pezron, E., Ricard, A., Lafuma, F. & Audebert, R. Reversible gel formation induced by ion complexation. 1. Borax-galactomannan interactions. Macromolecules 21, 1121–1125 (1988)

    Article  ADS  CAS  Google Scholar 

  5. Peppas, N. A., Huang, Y., Torres-Lugo, M., Ward, J. H. & Zhang, J. Physicochemical, foundations and structural design of hydrogels in medicine and biology. Annu. Rev. Biomed. Eng. 2, 9–29 (2000)

    Article  CAS  Google Scholar 

  6. Gong, J. P., Katsuyama, Y., Kurokawa, T. & Osada, Y. Double-network hydrogels with extremely high mechanical strength. Adv. Mater. 15, 1155–1158 (2003)

    Article  CAS  Google Scholar 

  7. Haraguchi, K. & Takehisa, T. Nanocomposite hydrogel: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv. Mater. 14, 1120–1124 (2002)

    Article  CAS  Google Scholar 

  8. Liu, Y. et al. High clay content nanocomposite hydrogels with surprising mechanical strength and interesting deswelling kinetics. Polymer 47, 1–5 (2006)

    Article  CAS  Google Scholar 

  9. Okada, A. & Usuki, A. Twenty years of polymer-clay nanocomposites. Macromol. Mater. Eng. 291, 1449–1476 (2006)

    Article  CAS  Google Scholar 

  10. Okay, O. & Oppermann, W. Polyacrylamide-clay nanocomposite hydrogel: rheological and light scattering characterization. Macromolecules 40, 3378–3387 (2007)

    Article  ADS  CAS  Google Scholar 

  11. Li, P., Siddaramaiah, Kim, N. H., Yoo, G. & Lee, J. Poly(acrylamide/laponite) nanocomposite hydrogels: swelling and cationic dye adsorption properties. J. Appl. Polym. Sci. 111, 1786–1798 (2009)

    Article  CAS  Google Scholar 

  12. Sijbesma, R. P. et al. Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 278, 1601–1604 (1997)

    Article  ADS  CAS  Google Scholar 

  13. Rockwood Additives Ltd. Laponite in Personal Care Products. Tech. Bull. L211/01g (1990)

  14. Ihre, H., Padilla De Jesus, O. L. & Fréchet, J. M. J. Fast and convenient divergent synthesis of aliphatic ester dendrimers by anhydride coupling. J. Am. Chem. Soc. 123, 5908–5917 (2001)

    Article  CAS  Google Scholar 

  15. Okuro, K., Kinbara, K., Tsumoto, K., Ishii, N. & Aida, T. Molecular glues carrying multiple guanidinium ion pendants via oligoether spacer: stabilization of microtubules against depolymerization. J. Am. Chem. Soc. 131, 1626–1627 (2009)

    Article  CAS  Google Scholar 

  16. Carnahan, M. A., Middleton, C., Kim, J., Kim, T. & Grinstaff, M. W. Hybrid dendritic-linear polyester-ethers for in situ photopolymerization. J. Am. Chem. Soc. 124, 5291–5293 (2002)

    Article  CAS  Google Scholar 

  17. Wathier, M., Jung, P. J., Carnahan, M. A., Kim, T. & Grinstaff, M. W. Dendritic macromers as in situ polymerizing biomaterials for securing cataract incisions. J. Am. Chem. Soc. 126, 12744–12745 (2004)

    Article  CAS  Google Scholar 

  18. Nowak, A. P. et al. Rapidly recovering hydrogel scaffolds from self-assembling diblock copolypeptide amphiphiles. Nature 417, 424–428 (2002)

    Article  ADS  CAS  Google Scholar 

  19. Yoshida, M. et al. Oligomeric electrolyte as a multifunctional gelator. J. Am. Chem. Soc. 129, 11039–11041 (2007)

    Article  CAS  Google Scholar 

  20. Xing, B. G. et al. Hydrophobic interaction and hydrogen bonding cooperatively confer a vancomycin hydrogel: a potential candidate for biomaterials. J. Am. Chem. Soc. 124, 14846–14847 (2002)

    Article  CAS  Google Scholar 

  21. Silva, G. A. et al. Selective differentiation of neural progenitor cells by high-epitope density nanofibers. Science 303, 1352–1355 (2004)

    Article  ADS  CAS  Google Scholar 

  22. Sreenivasachary, N. & Lehn, J. M. 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)

    Article  ADS  CAS  Google Scholar 

  23. Jayawarna, V. et al. Nanostructured hydrogels for three-dimensional cell culture through self-assembly of fluorenylmethoxycarbonyl-dipeptides. Adv. Mater. 18, 611–614 (2006)

    Article  CAS  Google Scholar 

  24. Schnepp, Z. A. C., Gonzalez-McQuire, R. & Mann, S. Hybrid biocomposites based on calcium phosphate mineralization of self-assembled supramolecular hydrogels. Adv. Mater. 18, 1869–1872 (2006)

    Article  CAS  Google Scholar 

  25. Rokita, B., Rosiak, J. M. & Ulanski, P. Ultrasound-induced cross-linking and formation of macroscopic covalent hydrogels in aqueous polymer and monomer solutions. Macromolecules 42, 3269–3274 (2009)

    Article  ADS  CAS  Google Scholar 

  26. Dong, L., Agarwal, A. K., Beebe, D. J. & Jiang, H. R. Adaptive liquid microlenses activated by stimuli-responsive hydrogels. Nature 442, 551–554 (2006)

    Article  ADS  CAS  Google Scholar 

  27. Ladet, S., David, L. & Domard, A. Multi-membrane hydrogels. Nature 452, 76–79 (2008)

    Article  ADS  CAS  Google Scholar 

  28. Kiyonaka, S. et al. Semi-wet peptide/protein array using supramolecular hydrogel. Nature Mater. 3, 58–64 (2004)

    Article  ADS  CAS  Google Scholar 

  29. Wang, Q. G., Yang, Z. M., Wang, L., Ma, M. L. & Xu, B. Molecular hydrogel-immobilized enzymes exhibit superactivity and high stability in organic solvents. Chem. Commun. 10, 1032–1034 (2007)

    Article  Google Scholar 

  30. Das, A. K., Collins, R. & Ulijn, R. V. Exploiting enzymatic (reversed) hydrolysis in directed self-assembly of peptide nanostructures. Small 4, 279–287 (2008)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Q.W. thanks the Japan Society for the Promotion of Science postdoctoral fellowship for foreign researchers. We thank Y. Arakawa for his support for the synthesis of PEG-G3-dendron.

Author Contributions Q.W. synthesized Gn-binders and analysed the properties of hydrogels; K.O. and K.K. noticed adhesion of guanidinium-ion-appended dendrimers to glass surfaces; M.Y. assisted the rheological studies; E.L. and M.L. performed cryogenic transmission electron microscopy; and T.A., J.L.M. and Q.W. designed the study, analysed the data and wrote the paper.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Justin L. Mynar or Takuzo Aida.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Methods, Supplementary Synthesis of Compounds 7, 9 and 11, Binders G1, G2 and G3 and PEG-G3-dendron (25), a Supplementary Reference, Oxidation of o-Phenylenediamine with H202 Catayzed Myoglobin (Mb) and Supplementary Figures S1- S8 with Legends. (PDF 13251 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wang, Q., Mynar, J., Yoshida, M. et al. High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder. Nature 463, 339–343 (2010). https://doi.org/10.1038/nature08693

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature08693

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing