Hydrogels with rapid mechanical energy-dissipation capability are highly desirable for protective and shock-absorbing applications. However, conventional systems often suffer from irreversible network damage, slow recovery, and mechanical fatigue. Herein, we report a biodegradable supramolecularly crosslinked polymer hydrogel (AGK) engineered through the synergistic integration of boronate ester covalent networks and G4-quartet supramolecular assemblies. The coupled covalent–supramolecular interactions promote reversible network dissociation and adaptive molecular reorganization under mechanical stress, enabling rapid self-healing, enhanced structural integrity, and efficient energy dissipation. The AGK hydrogel withstands compressive loads up to ∼5.4 kg, significantly outperforming the pristine biopolymer hydrogel (∼2.9 kg). Dynamic impact analyses reveal a remarkably low coefficient of restitution (∼0.21), substantially lower than those of conventional polymeric materials, demonstrating superior impact attenuation and rapid mechanical energy dissipation. Consequently, the hydrogel effectively protects fragile objects from both static compression and free-fall impact damage while maintaining mechanical resilience over repeated damage–recovery cycles. This work establishes a sustainable supramolecular engineering strategy for designing adaptive self-healable hydrogels with efficient energy-dissipation capability, offering promising opportunities for advanced protective, impact-mitigating, and mechanically adaptive soft materials.
| [1] |
S. Fuchs, K. Shariati, and M. Ma, “Specialty Tough Hydrogels and Their Biomedical Applications,” Advanced Healthcare Materials 9 (2020): 1901396.
|
| [2] |
X. Kuang, M. O. Arıcan, T. Zhou, X. Zhao, and Y. S. Zhang, “Functional Tough Hydrogels: Design, Processing, and Biomedical Applications,” Accounts of Materials Research 4 (2023): 101–114.
|
| [3] |
N. Petelinšek and S. Mommer, “Tough Hydrogels for Load-Bearing Applications,” Advanced Science 11 (2024): 2307404.
|
| [4] |
Y. Liu and Z. Guo, “Small Functional Hydrogels With Big Engineering Applications,” Materials Today Physics 43 (2024): 101397.
|
| [5] |
T. Aida, E. W. Meijer, and S. I. Stupp, “Functional Supramolecular Polymers,” Science 335 (2012): 813–817.
|
| [6] |
Q. Zhang, C. Y. Shi, D. H. Qu, Y. T. Long, B. L. Feringa, and H. Tian, “Exploring a Naturally Tailored Small Molecule for Stretchable, Self-healing, and Adhesive Supramolecular Polymers,” Science Advances 4 (2018): eaat8192.
|
| [7] |
M. Wu, L. Han, B. Yan, and H. Zeng, “Self-healing Hydrogels Based on Reversible Noncovalent and Dynamic Covalent Interactions: A Short Review,” Supramolecular Materials 2 (2023): 100045.
|
| [8] |
S. Khattak, I. Ullah, H. Xie, X. D. Tao, H. T. Xu, and J. Shen, “Self-healing Hydrogels as Injectable Implants: Advances in Translational Wound Healing,” Coordination Chemistry Reviews 509 (2024): 215790.
|
| [9] |
J. Xie, P. Yu, Z. Wang, and J. Li, “Recent Advances of Self-healing Polymer Materials via Supramolecular Forces for Biomedical Applications,” Biomacromolecules 23 (2022): 641–660.
|
| [10] |
P. Singh, V. K. Golla, N. Sharma, and N. Chaudhri, “A Comprehensive Review on the Advancement of Supramolecular Polymers and Their Pharmaceutical and Biomedical Applications,” Coordination Chemistry Reviews 548 (2026): 217223.
|
| [11] |
Z. Li, R. Yu, and B. Guo, “Shape-memory and Self-healing Polymers Based on Dynamic Covalent Bonds and Dynamic Noncovalent Interactions: Synthesis, Mechanism, and Application,” ACS Applied Bio Materials 4 (2021): 5926–5943.
|
| [12] |
Z. Lei, H. Chen, S. Huang, L. J. Wayment, Q. Xu, and W. Zhang, “New Advances in Covalent Network Polymers via Dynamic Covalent Chemistry,” Chemical Reviews 124 (2024): 7829–7906.
|
| [13] |
J. J. Q. Mah, N. E. B. Surat'man, B. Li, S. Wang, and Z. Li, “Recent Advances of Dynamic Covalent Chemistry Polymers Aligning With Principles of Green Chemistry,” ChemSusChem 18 (2025): e202500480.
|
| [14] |
S. Cho, S. Y. Hwang, D. X. Oh, and J. Park, “Recent Progress in Self-healing Polymers and Hydrogels Based on Reversible Dynamic B–O Bonds: Boronic/Boronate Esters, Borax, and Benzoxaborole,” Journal of Materials Chemistry A 9 (2021): 14630–14655.
|
| [15] |
S. Laquerbe, J. Es Sayed, C. Lorthioir, et al., “Supramolecular Crosslinked Hydrogels: Similarities and Differences With Chemically Crosslinked Hydrogels,” Macromolecules 56 (2023): 7406–7418.
|
| [16] |
T. Bhattacharyya, P. Saha, and J. Dash, “Guanosine-Derived Supramolecular Hydrogels: Recent Developments and Future Opportunities,” ACS Omega 3 (2018): 2230–2241.
|
| [17] |
G. M. Peters, L. P. Skala, T. N. Plank, et al., “G4-Quartet·M+ Borate Hydrogels,” Journal of the American Chemical Society 137 (2015): 5819–5827.
|
| [18] |
R. C. Ollier and M. J. Webber, “Mechanoresponsive Hydrogels Emerging From Dynamic and Non-Covalent Interactions,” Advanced Materials 37 (2025): 2507397.
|
| [19] |
H. Yin, F. Liu, T. Abdiryim, and X. Liu, “Self-healing Hydrogels: From Synthesis to Multiple Applications,” ACS Materials Letters 5 (2023): 1787–1830.
|
| [20] |
Q. Wang, Y. Zhang, Y. Ma, M. Wang, and G. Pan, “Nano-crosslinked Dynamic Hydrogels for Biomedical Applications,” Materials Today Bio 20 (2023): 100640.
|
| [21] |
B. Li, P. F. Cao, T. Saito, and A. P. Sokolov, “Intrinsically Self-healing Polymers: From Mechanistic Insight to Current Challenges,” Chemical Reviews 123 (2023): 701–735.
|
| [22] |
L. Jia, R. Liu, J. Lv, et al., “Probing the Interactions of GlcNH2 With Boric Acid via NMR Spectroscopy,” Physical Chemistry Chemical Physics 23 (2021): 15758–15765.
|
| [23] |
W. Zhou, Z. Yu, G. Ma, et al., “Thioflavin T Specifically Brightening “Guanine Island” in Duplex-DNA: A Novel Fluorescent Probe for Single-nucleotide Mutation,” Analyst 144 (2019): 2284–2290.
|
| [24] |
F. Carducci, J. S. Yoneda, R. Itri, and P. Mariani, “On the Structural Stability of Guanosine-based Supramolecular Hydrogels,” Soft Matter 14 (2018): 2938–2948.
|
| [25] |
K. Bertula, L. Martikainen, P. Munne, et al., “Strain-stiffening of Agarose Gels,” ACS Macro Letters 8 (2019): 670–675.
|
| [26] |
T. Ghosh and A. K. Das, “Dynamic Boronate Esters Cross-linked Guanosine Hydrogels: A Promising Biomaterial for Emergent Applications,” Coordination Chemistry Reviews 488 (2023): 215170.
|
| [27] |
K. Hyun, S. H. Kim, K. H. Ahn, and S. J. Lee, “Large Amplitude Oscillatory Shear as a Way to Classify the Complex Fluids,” Journal of Non-Newtonian Fluid Mechanics 107 (2002): 51–65.
|
| [28] |
S. H. Siddique, P. J. Hazell, H. Wang, J. P. Escobedo, and A. A. H. Ameri, “Lessons From Nature: 3D Printed Bio-inspired Porous Structures for Impact Energy Absorption—A Review,” Additive manufacturing 58 (2022): 103051.
|
| [29] |
M. Khodadadi Yazdi, A. Taghizadeh, M. Taghizadeh, et al., “Agarose-based Biomaterials for Advanced Drug Delivery,” Journal of Controlled Release 326 (2020): 523–543.
|
| [30] |
M. I. Patiño Vargas, F. D. Martinez-Garcia, F. Offens, et al., “Viscoelastic Properties of Plasma-Agarose Hydrogels Dictate Favorable Fibroblast Responses for Skin Tissue Engineering Applications,” Biomaterials Advances 139 (2022): 212967.
|
| [31] |
I. Yardeny, D. Portnikov, and H. Kalman, “Experimental Investigation of the Coefficient of Restitution of Particles Colliding With Surfaces in Air and Water,” Advanced Powder Technology 31 (2020): 3747–3759.
|
| [32] |
A. Castiglioni, L. Castellani, G. Cuder, and S. Comba, “Relevant Materials Parameters in Cushioning for EPS Foams,” Colloids and Surfaces A: Physicochemical and Engineering Aspects 534 (2017): 71–77.
|
| [33] |
P. Böröcz and Z. Németh, “Review Paper on the Field Measurement of Parcel Packaging Drop for Testing Purposes,” Packaging Technology and Science 38 (2025): 345–357.
|
| [34] |
S. Ganesh, S. N. Subraveti, and S. R. Raghavan, “How a Gel Can Protect an Egg: A Flexible Hydrogel With Embedded Starch Particles Shields Fragile Objects Against Impact,” ACS Applied Materials & Interfaces 14 (2022): 20014–20022.
|
| [35] |
Y. Yu, J. Hu, W. Li, H. Zhang, and Z. Wang, “Highly Efficient and Reusable Hydrogel-based Packaging Material Enabled by Oriented Porous Structures and Hybrid Dual-cross-linking Networks,” ACS Applied Polymer Materials 7 (2025): 11986–11997.
|
| [36] |
Z. Zhuang, Z. Qian, X. Wang, et al., “Bioinspired Structural Composite Flexible Material With High Cushion Performance,” Advanced Science 11 (2024): 2304947.
|
| [37] |
S. Bonardd, M. Nandi, J. I. Hernández García, B. Maiti, A. Abramov, and D. Díaz Díaz, “Self-healing Polymeric Soft Actuators,” Chemical Reviews 123 (2022): 736–810.
|
| [38] |
M. Qi, R. Yang, Z. Wang, et al., “Bioinspired Self-Healing Soft Electronics,” Advanced Functional Materials 33 (2023): 2214479.
|
| [39] |
J. Kang, J. B. H. Tok, and Z. Bao, “Self-healing Soft Electronics,” Nature Electronics 2 (2019): 144–150.
|
| [40] |
Z. Li, L. Chen, F. Liu, and X. Liu, “Chitosan-based Hydrogels With Stretchable, Self-healing, Self-adhesive Properties for Flexible Sensing Applications,” Colloids and Surfaces A: Physicochemical and Engineering Aspects 726 (2025): 138095.
|
| [41] |
H. Yin, F. Liu, T. Abdiryim, J. Chen, and X. Liu, “Sodium Carboxymethyl Cellulose and MXene Reinforced Multifunctional Conductive Hydrogels for Multimodal Sensors and Flexible Supercapacitors,” Carbohydrate Polymers 327 (2023): 121677.
|
| [42] |
Z. Xu, J. Lu, D. Lu, et al., “Rapidly Damping Hydrogels Engineered Through Molecular Friction,” Nature Communications 15 (2024): 4895.
|
| [43] |
B. Xiong, R. D. Loss, D. Shields, et al., “Polyacrylamide Degradation and Its Implications in Environmental Systems,” npj Clean Water 1 (2018): 17.
|
| [44] |
K. D. Nixon, Z. O. G. Schyns, Y. Luo, et al., “Analyses of Circular Solutions for Advanced Plastics Waste Recycling,” Nature Chemical Engineering 1 (2024): 615–626.
|
Rights & permissions
2026 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.
PDF
(3129KB)
