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Highly compressible glass-like supramolecular polymer networks


Supramolecular polymer networks are non-covalently crosslinked soft materials that exhibit unique mechanical features such as self-healing, high toughness and stretchability. Previous studies have focused on optimizing such properties using fast-dissociative crosslinks (that is, for an aqueous system, dissociation rate constant kd > 10 s1). Herein, we describe non-covalent crosslinkers with slow, tuneable dissociation kinetics (kd < 1 s−1) that enable high compressibility to supramolecular polymer networks. The resultant glass-like supramolecular networks have compressive strengths up to 100 MPa with no fracture, even when compressed at 93% strain over 12 cycles of compression and relaxation. Notably, these networks show a fast, room-temperature self-recovery (< 120 s), which may be useful for the design of high-performance soft materials. Retarding the dissociation kinetics of non-covalent crosslinks through structural control enables access of such glass-like supramolecular materials, holding substantial promise in applications including soft robotics, tissue engineering and wearable bioelectronics.

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Fig. 1: Design of glass-like SPNs.
Fig. 2: Thermodynamic and kinetic properties of slow-dissociative non-covalent crosslinks.
Fig. 3: Rheological characterization of glass-like SPNs.
Fig. 4: Evaluation of compressive properties of glass-like SPNs.
Fig. 5: Demonstration of rapid self-recovery of glass-like SPNs and their application.

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Data availability

Data generated and analysed during this study are provided as source data with this paper or included in the Supplementary Information. Further data are available from the corresponding authors upon request.


  1. Seiffert, S. & Sprakel, J. Physical chemistry of supramolecular polymer networks. Chem. Soc. Rev. 41, 909–930 (2012).

    Article  CAS  Google Scholar 

  2. Voorhaar, L. & Hoogenboom, R. Supramolecular polymer networks: hydrogels and bulk materials. Chem. Soc. Rev. 45, 4013–4031 (2016).

    Article  CAS  Google Scholar 

  3. Sun, T. L. et al. Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity. Nat. Mater. 12, 932–937 (2013).

    Article  CAS  Google Scholar 

  4. Wu, Y. et al. Biomimetic supramolecular fibers exhibit water-induced supercontraction. Adv. Mater. 30, 1707169 (2018).

    Article  Google Scholar 

  5. Jeon, I., Cui, J., Illeperuma, W. R. K., Aizenberg, J. & Vlassak, J. J. Extremely stretchable and fast self-healing hydrogels. Adv. Mater. 28, 4678–4683 (2016).

    Article  CAS  Google Scholar 

  6. Li, C.-H. et al. A highly stretchable autonomous self-healing elastomer. Nat. Chem. 8, 618–624 (2016).

    Article  CAS  Google Scholar 

  7. Sun, G., Li, Z., Liang, R., Weng, L.-T. & Zhang, L. Super stretchable hydrogel achieved by non-aggregated spherulites with diameters <5 nm. Nat. Commun. 7, 12095 (2016).

    Article  Google Scholar 

  8. Cordier, P., Tournilhac, F., Soulié-Ziakovic, C. & Leibler, L. Self-healing and thermoreversible rubber from supramolecular assembly. Nature 451, 977–980 (2008).

    Article  CAS  Google Scholar 

  9. Chen, Y., Kushner, A. M., Williams, G. A. & Guan, Z. Multiphase design of autonomic self-healing thermoplastic elastomers. Nat. Chem. 4, 467–472 (2012).

    Article  CAS  Google Scholar 

  10. Yanagisawa, Y., Nan, Y., Okuro, K. & Aida, T. Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking. Science 359, 72–76 (2018).

    Article  CAS  Google Scholar 

  11. Qin, B. et al. Tough and multi-recyclable cross-linked supramolecular polyureas via incorporating noncovalent bonds into main-chains. Adv. Mater. 32, 2000096 (2020).

    Article  CAS  Google Scholar 

  12. Wang, C. et al. Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. Nat. Chem. 5, 1042–1048 (2013).

    Article  CAS  Google Scholar 

  13. Choi, S., Kwon, T.-w, Coskun, A. & Choi, J. W. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science 357, 279–283 (2017).

    Article  CAS  Google Scholar 

  14. Tee, B. C.-K., Wang, C., Allen, R. & Bao, Z. An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications. Nat. Nanotechnol. 7, 825–832 (2012).

    Article  CAS  Google Scholar 

  15. Liu, K., Jiang, Y., Bao, Z. & Yan, X. Skin-inspired electronics enabled by supramolecular polymeric materials. CCS Chem. 1, 431–447 (2019).

    Article  CAS  Google Scholar 

  16. Dankers, P. Y. W. et al. Hierarchical formation of supramolecular transient networks in water: a modular injectable delivery system. Adv. Mater. 24, 2703–2709 (2012).

    Article  CAS  Google Scholar 

  17. Zhang, S. et al. A ph-responsive supramolecular polymer gel as an enteric elastomer for use in gastric devices. Nat. Mater. 14, 1065–1071 (2015).

    Article  CAS  Google Scholar 

  18. Yount, W. C., Loveless, D. M. & Craig, S. L. Strong means slow: dynamic contributions to the bulk mechanical properties of supramolecular networks. Angew. Chem. Int. Ed. 44, 2746–2748 (2005).

    Article  CAS  Google Scholar 

  19. Yount, W. C., Loveless, D. M. & Craig, S. L. Small-molecule dynamics and mechanisms underlying the macroscopic mechanical properties of coordinatively cross-linked polymer networks. J. Am. Chem. Soc. 127, 14488–14496 (2005).

    Article  CAS  Google Scholar 

  20. Grindy, S. C. et al. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics. Nat. Mater. 14, 1210–1216 (2015).

    Article  CAS  Google Scholar 

  21. Appel, E. A., del Barrio, J., Loh, X. J. & Scherman, O. A. Supramolecular polymeric hydrogels. Chem. Soc. Rev. 41, 6195–6214 (2012).

    Article  CAS  Google Scholar 

  22. Xia, D. et al. Functional supramolecular polymeric networks: the marriage of covalent polymers and macrocycle-based host-guest interactions. Chem. Rev. 120, 6070–6123 (2020).

    Article  CAS  Google Scholar 

  23. Wang, L. et al. A self-cross-linking supramolecular polymer network enabled by crown-ether-based molecular recognition. J. Am. Chem. Soc. 142, 2051–2058 (2020).

    Article  CAS  Google Scholar 

  24. Shi, C.-Y. et al. An ultrastrong and highly stretchable polyurethane elastomer enabled by a zipper-like ring-sliding effect. Adv. Mater. 32, 2000345 (2020).

    Article  CAS  Google Scholar 

  25. Harada, A., Kobayashi, R., Takashima, Y., Hashidzume, A. & Yamaguchi, H. Macroscopic self-assembly through molecular recognition. Nat. Chem. 3, 34–37 (2011).

    Article  CAS  Google Scholar 

  26. Gotoh, H. et al. Optically transparent, high-toughness elastomer using a polyrotaxane cross-linker as a molecular pulley. Sci. Adv. 4, eaat7629 (2018).

    Article  CAS  Google Scholar 

  27. Ogoshi, T., Kayama, H., Yamafuji, D., Aoki, T. & Yamagishi, T.-a Supramolecular polymers with alternating pillar[5]arene and pillar[6]arene units from a highly selective multiple host–guest complexation system and monofunctionalized pillar[6]arene. Chem. Sci. 3, 3221–3226 (2012).

    Article  CAS  Google Scholar 

  28. Li, Z.-Y. et al. Cross-linked supramolecular polymer gels constructed from discrete multi-pillar[5]arene metallacycles and their multiple stimuli-responsive behavior. J. Am. Chem. Soc. 136, 8577–8589 (2014).

    Article  CAS  Google Scholar 

  29. Wang, X.-H. et al. Efficient aggregation-induced emission manipulated by polymer host materials. Adv. Mater. 31, 1903962 (2019).

    Article  Google Scholar 

  30. Xu, W., Song, Q., Xu, J.-F., Serpe, M. J. & Zhang, X. Supramolecular hydrogels fabricated from supramonomers: a novel wound dressing material. ACS Appl. Mater. Interfaces 9, 11368–11372 (2017).

    Article  CAS  Google Scholar 

  31. Liu, J. et al. Tough supramolecular polymer networks with extreme stretchability and fast room-temperature self-healing. Adv. Mater. 29, 1605325 (2017).

    Article  Google Scholar 

  32. Lee, J. W., Samal, S., Selvapalam, N., Kim, H.-J. & Kim, K. Cucurbituril homologues and derivatives:new opportunities in supramolecular chemistry. Acc. Chem. Res. 36, 621–630 (2003).

    Article  CAS  Google Scholar 

  33. Lagona, J., Mukhopadhyay, P., Chakrabarti, S. & Isaacs, L. The cucurbit[n]uril family. Angew. Chem. Int. Ed. 44, 4844–4870 (2005).

    Article  CAS  Google Scholar 

  34. Urbach, A. R. & Ramalingam, V. Molecular recognition of amino acids, peptides, and proteins by cucurbit[n]uril receptors. Isr. J. Chem. 51, 664–678 (2011).

    Article  CAS  Google Scholar 

  35. Ni, X.-L. et al. Cucurbit[n]uril-based coordination chemistry: from simple coordination complexes to novel poly-dimensional coordination polymers. Chem. Soc. Rev. 42, 9480–9508 (2013).

    Article  CAS  Google Scholar 

  36. Assaf, K. I. & Nau, W. M. Cucurbiturils: from synthesis to high-affinity binding and catalysis. Chem. Soc. Rev. 44, 394–418 (2015).

    Article  CAS  Google Scholar 

  37. Barrow, S. J., Kasera, S., Rowland, M. J., del Barrio, J. & Scherman, O. A. Cucurbituril-based molecular recognition. Chem. Rev. 115, 12320–12406 (2015).

    Article  CAS  Google Scholar 

  38. Huang, Z. et al. Host-enhanced phenyl-perfluorophenyl polar-π interactions. J. Am. Chem. Soc. 142, 7356–7361 (2020).

    Article  CAS  Google Scholar 

  39. Biedermann, F., Vendruscolo, M., Scherman, O. A., De Simone, A. & Nau, W. M. Cucurbit [8] uril and blue-box: high-energy water release overwhelms electrostatic interactions. J. Am. Chem. Soc. 135, 14879–14888 (2013).

    Article  CAS  Google Scholar 

  40. Bell, R. P. & Hinshelwood, C. N. The theory of reactions involving proton transfers. Proc. Math. Phys. Eng. Sci. 154, 414–429 (1936).

    Google Scholar 

  41. Evans, M. G. & Polanyi, M. Further considerations on the thermodynamics of chemical equilibria and reaction rates. Trans. Faraday Soc. 32, 1333–1360 (1936).

    Article  CAS  Google Scholar 

  42. Burnouf, D. et al. kinitc: a new method for obtaining joint thermodynamic and kinetic data by isothermal titration calorimetry. J. Am. Chem. Soc. 134, 559–565 (2012).

    Article  CAS  Google Scholar 

  43. Huang, Z. et al. Supramolecular chemistry of cucurbiturils: tuning cooperativity with multiple noncovalent interactions from positive to negative. Langmuir 32, 12352–12360 (2016).

    Article  CAS  Google Scholar 

  44. Sheppard, J. & Clapson, W. Compression stress strain of rubber. Rubber Chem. Technol. 6, 126–150 (1933).

    Article  Google Scholar 

  45. Elleuch, R., Elleuch, K., Salah, B. & Zahouani, H. Tribological behavior of thermoplastic polyurethane elastomers. Mater. Des. 28, 824–830 (2007).

    Article  CAS  Google Scholar 

  46. Gerratt, A. P., Michaud, H. O. & Lacour, S. P. Elastomeric electronic skin for prosthetic tactile sensation. Adv. Func. Mater. 25, 2287–2295 (2015).

    Article  CAS  Google Scholar 

  47. Lee, W., Yeo, K., Andriyana, A., Shee, Y. & Adikan, F. M. Effect of cyclic compression and curing agent concentration on the stabilization of mechanical properties of pdms elastomer. Mater. Des. 96, 470–475 (2016).

    Article  CAS  Google Scholar 

  48. Park, J. et al. Extremely rapid self-healable and recyclable supramolecular materials through planetary ball milling and host–guest interactions. Adv. Mater. 32, 2002008 (2020).

    Article  CAS  Google Scholar 

  49. Hammock, M. L., Chortos, A., Tee, B. C.-K., Tok, J. B.-H. & Bao, Z. 25th anniversary article: the evolution of electronic skin (e-skin): a brief history, design considerations, and recent progress. Adv. Mater. 25, 5997–6038 (2013).

    Article  CAS  Google Scholar 

  50. Chortos, A., Liu, J. & Bao, Z. Pursuing prosthetic electronic skin. Nat. Mater. 15, 937–950 (2016).

    Article  CAS  Google Scholar 

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O.A.S. and G.W. acknowledge the Leverhulme Trust Program Grant (Natural Materials Innovation). Z.H. acknowledges the Marie Skłodowska-Curie Fellowship (no. 845640). X.C. acknowledges Cambridge Display Technology (CDT) for financial support. D.J.W. thanks the Engineering and Physical Sciences Research Council for a PhD studentship (grant no. EP/R512461/1). We thank G.G. Malliaras for helpful discussions.

Author information

Authors and Affiliations



Z.H. and O.A.S. conceived the idea. Z.H., X.C., S.J.K.O., G.W., D.J.W., J.A.M. and O.A.S. designed the experiments. Z.H. executed most of the experiments and analysed the data. X.C., S.J.K.O., G.W., D.J.W., J.L. and J.A.M. helped perform some of the experiments and data analysis. Z.H., J.A.M. and O.A.S. wrote the paper. All authors discussed the experiments, edited the paper and gave consent for this publication under the supervision of O.A.S.

Corresponding author

Correspondence to Oren A. Scherman.

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The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks Richard Hoogenboom, Rebecca Kramer-Bottiglio and Mathew Webber for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Charts 1 and 2, Figs. 1–41, Tables 1–5 and description of Videos 1–6.

Supplementary Video 1

Compressive test: 100 MPa.

Supplementary Video 2

Compressive test: 1.0 GPa.

Supplementary Video 3

Human compression demo.

Supplementary Video 4

Car-compression demo.

Supplementary Video 5

Ionic conductor demo.

Supplementary Video 6

Ball-drop demo.

Source data

Source Data Fig. 2

Source data in tables for Fig. 2 in the main text.

Source Data Fig. 3

Source data in tables for Fig. 3 in the main text.

Source Data Fig. 4

Source data in tables for Fig. 4 in the main text.

Source Data Fig. 5

Source data in tables for Fig. 5 in the main text.

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Huang, Z., Chen, X., O’Neill, S.J.K. et al. Highly compressible glass-like supramolecular polymer networks. Nat. Mater. 21, 103–109 (2022).

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