Skip to main content
Log in

Light- and pH-responsive self-healing hydrogel

  • Polymers
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

A self-healing hydrogel was synthesized via the multi-component reaction of azobenzene-methacrylamide, β-CD and 3-methacrylamido phenylboronic acid. The orthogonal method was applied to analyze the influence of host–guest inclusion complexation, cross-linker and phenylboronic acid monomers content on mechanical properties and healing efficiency of the hydrogel. The results indicated that hydrogel showed autonomic self-healing behavior. The hydrogel demonstrated light-switchable self-healing ability and pH-sensitive swelling ratio. It was found that hydrogel showed high elongation, excellent resilience and low elastic hysteresis. The design of the combined host–guest interactions and boronate esters on the hydrogel showed advantage for improving the mechanical, self-healing and recovery properties simultaneously.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

Similar content being viewed by others

References

  1. Wei Z, Yang JH, Zhou J, Xu F, Zrínyi M, Dussault PH, Osadag Y, Chen YM (2014) Self- healing gels based on constitutional dynamic chemistry and their potential applications. Chem Soc Rev 43:8114–8131

    Article  Google Scholar 

  2. Taylor DL (2016) M. in het Panhuis. Self-healing hydrogels. Adv Mater 28:9060–9093

    Article  Google Scholar 

  3. Yang Y, Urban MW (2013) Self-healing polymeric materials. Chem Soc Rev 42:7446–7467

    Article  Google Scholar 

  4. Phadke A, Zhang C, Arman B, Hsu C, Mashelkar RA, Lele AK, Tauber MJ, Arya G, Varghese S (2012) Rapid self-healing hydrogels. Proc Natl Acad Sci USA 109:4383–4388

    Article  Google Scholar 

  5. Bai T, Liu S, Sun F, Sinclair A, Zhang L, Shao Q, Jiang S (2014) Zwitterionic fusion in hydrogels and spontaneous and time-independent self-healing under physiological conditions. Biomaterials 35:3926–3933

    Article  Google Scholar 

  6. Zhang Z, Li T, Chen B, Wang S, Guo Z (2017) Self-healing supramolecular hydrogel of poly(vinyl alcohol)/chitosan carbon dots. J Mater Sci 52:10614–10623. https://doi.org/10.1007/s10853-017-1222-3

    Article  Google Scholar 

  7. Gao Z, Duan L, Yang Y, Hu W, Gao G (2018) Mussel-inspired tough hydrogels with self-repairing and tissue adhesion. Appl Surf Sci 427:74–82

    Article  Google Scholar 

  8. Hussain I, Sayed SM, Liu S, Yao F, Oderinde O, Fu G (2018) Hydroxyethyl cellulose-based self-healing hydrogels with enhanced mechanical properties via metal-ligand bond interactions. Eur Polym J 100:219–227

    Article  Google Scholar 

  9. Kakuta T, Takashima Y, Nakahata M, Otsubo M, Yamaguchi H, Harada A (2013) Preorganized hydrogel: self-healing properties of supramolecular hydrogels formed by polymerization of host-guest-monomers that contain cyclodextrins and hydrophobic guest groups. Adv Mater 25:2849–2853

    Article  Google Scholar 

  10. Takashima Y, Yonekura K, Koyanagi K, Iwaso K, Nakahata M, Yamaguchi H, Harada A (2017) Multifunctional stimuli-responsive supramolecular materials with stretching, coloring, and self-healing properties functionalized via host-guest interactions. Macromolecules 50:4144–4150

    Article  Google Scholar 

  11. Xuan H, Ren J, Zhang J, Ge L (2017) Novel highly-flexible, acid-resistant and self-healing host-guest transparent multilayer films. Appl Surf Sci 411:303–314

    Article  Google Scholar 

  12. Tuncaboylu DC, Sahin M, Argun A, Oppermann W, Okay O (2012) Dynamics and large strain behavior of self-healing hydrogels with and without surfactants. Macromolecules 45:1991–2000

    Article  Google Scholar 

  13. Rao Z, Inoue M, Matsuda M, Taguchi T (2011) Quick self-healing and thermo-reversible liposome gel. Colloids Surf B 82:196–202

    Article  Google Scholar 

  14. Cui W, Ji J, Cai Y, Li H, Ran R (2015) Robust, anti-fatigue, and self-healing graphene oxide/hydrophobically associated composite hydrogels and their use as recyclable adsorbents for dye wastewater treatment. J Mater Chem A 3:17445–17458

    Article  Google Scholar 

  15. Sano K, Kawamura R, Tominaga T, Oda N, Ijiro K, Osada Y (2011) Self-repairing filamentous actin hydrogel with hierarchical structure. Biomacromolecules 12:4173–4177

    Article  Google Scholar 

  16. Zhang Y, An R, Han L, Wang X, Shi L, Ran R (2018) Novel self-healing, shape-memory, tunable double-layer actuators based on semi-IPN and physical double-network hydrogels. Macromol Mater Eng 303:1800505

    Article  Google Scholar 

  17. Yoon JA, Kamada J, Koynov K, Mohin J, Nicolay R, Zhang Y, Balazs AC, Kowalewski T, Matyjaszewski K (2011) Self-healing polymer films based on thiol-disulfide exchange reactions and self-healing kinetics measured using atomic force microscopy. Macromolecules 45:142–149

    Article  Google Scholar 

  18. Zhou L, Zhang G, Feng Y, Zhang H, Li J, Shi X (2018) Design of a self-healing and flame-retardant cyclotriphosphazene-based epoxy vitrimer. J Mater Sci 53:7030–7047. https://doi.org/10.1007/s10853-018-2015-z

    Article  Google Scholar 

  19. Cash JJ, Kubo T, Bapat AP, Sumerlin BS (2015) Room-temperature self-healing polymers based on dynamic covalent boronic esters. Macromolecules 48:2098–2106

    Article  Google Scholar 

  20. Amaral AJR, Emamzadeh M, Pasparakis G (2018) Transiently malleable multi-healable hydrogel nanocomposites based on responsive boronic acid copolymers. Polym Chem 9:525–537

    Article  Google Scholar 

  21. Zhang Y, Tao L, Li S, Wei Y (2011) Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules. Biomacromolecules 12:2894–2901

    Article  Google Scholar 

  22. Deng G, Tang C, Li F, Jiang H, Chen Y (2010) Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties. Macromolecules 43:1191–1194

    Article  Google Scholar 

  23. Zhao L, Jiang B, Huang Y (2018) Self-healable polysiloxane/graphene nanocomposite and its application in pressure sensor. J Mater Sci 54:5472–5483. https://doi.org/10.1007/s10853-018-03233-6

    Article  Google Scholar 

  24. Hu C, An R, Han L, Wang X, Shi Y, Ran R (2018) Preparation of high strength double physically cross-linked hydrogels by immersion method—how to avoid uneven soaking. Colloids Surf A 559:74–82

    Article  Google Scholar 

  25. Hu C, Zhang Y, Wang X, Xing L, Shi L, Ran R (2018) Stable, strain-sensitive conductive hydrogel with antifreezing capability, remoldability, and reusability. ACS Appl Mater Interfaces 10:44000–44010

    Article  Google Scholar 

  26. Yang Q, Wang P, Zhao C, Wang W, Yang J, Liu Q (2017) Light-switchable self-healing hydrogel based on host-guest macro-crosslinking. Macromol Rapid Commun 38:1600741

    Article  Google Scholar 

  27. Sugnaux C, Klok H-A (2014) Glucose-sensitive QCM-sensors via direct surface RAFT polymerization. Macromol Rapid Commun 35:1402–1407

    Article  Google Scholar 

  28. Zheng P, Hu X, Zhao X, Li L, Tam KC, Gan LH (2004) Photoregulated sol-gel transition of novel azobenzene-functionalized hydroxypropyl methylcellulose and its α-cyclodextrin complexes. Macromol Rapid Commun 25:678–682

    Article  Google Scholar 

  29. Jin Q, Luy C, Ji J, Agarwal S (2012) Design and proof of reversible micelle-to-vesicle multistimuli-responsive morphological regulations. J Polym Sci Part A Polym Chem 50:451–457

    Article  Google Scholar 

  30. Springsteen G, Wang B (2002) A detailed examination of boronic acid–diol complexation. Tetrahedron 58:5291–5300

    Article  Google Scholar 

  31. Bueno VB, Bentini R, Catalani LH, Petri DFS (2013) Synthesis and swelling behavior of xanthan-based hydrogels. Carbohyd Polym 92:1091–1099

    Article  Google Scholar 

  32. Diani J, Fayolle B, Gilormini P (2009) A review on the Mullins effect. Eur Polym J 45:601–612

    Article  Google Scholar 

  33. Zhang L, Zhao J, Zhu J, He C, Wang H (2012) Anisotropic tough poly(vinyl alcohol) hydrogels. Soft Matter 8:10439–10447

    Article  Google Scholar 

  34. Webber RE, Creton C, Brown HR, Gong JP (2007) Large strain hysteresis and Mullins effect of tough double-network hydrogels. Macromolecules 40:2919–2927

    Article  Google Scholar 

  35. Su C, Su Y, Li Z, Haq MA, Zhou Y, Wang D (2017) In situ synthesis of bilayered gradient poly(vinyl alcohol)/hydroxyapatite composite hydrogel by directional freezing-thawing and electrophoresis method. Mater Sci Eng C 77:76–83

    Article  Google Scholar 

  36. Zhu M, Liu Y, Sun B, Zhang W, Liu X, Yu H, Zhang Y, Kuckling D, Adler H-JP (2006) A novel highly resilient nanocomposite hydrogel with low hysteresis and ultrahigh elongation. Macromol Rapid Commun 27:1023–1028

    Article  Google Scholar 

Download references

Acknowledgements

This work is partially supported by the National Natural Science Foundation of China (Grant 21304075), Beijing Key Laboratory of Quality Evaluation Technology for Hygiene and Safety of Plastics (Beijing Technology and Business University) (Grant SS201707), Beijing National Laboratory for Molecular Science, China Scholarship Council Fellowship (Grant 201706970002) and the “Top-rated Discipline” construction scheme of Shaanxi higher education.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Pengxiang Jia or Yang Zhang.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 1049 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, M., Wang, L., Cheng, Y. et al. Light- and pH-responsive self-healing hydrogel. J Mater Sci 54, 9983–9994 (2019). https://doi.org/10.1007/s10853-019-03547-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-019-03547-z

Navigation