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Abstract Cell engineering, soft robotics, and wearable electronics often desire soft materials that are easy to deform, self‐heal readily, and can relax stress rapidly. Hydrogels, a type of hydrophilic networks, are such kind of materials that can be made responsive to environmental stimuli. However, conventional hydrogels often suffer from poor stretchability and repairability. Here, hydrogels consisting of boronic ester dynamic covalent bonds in a double network of poly(vinyl alcohol)/boric acid and chitosan are synthesized, which demonstrate extreme stretchability (up to 310 times the original length), instant self‐healing (within 5 s), and reusability and inherent adhesion. Their instant stress relaxation stems from a low activation energy of the boronic ester bond exchange (≤20 kJ mol−1) and contributes to the extreme stretchability and self‐healing behaviors. Various water‐dispersible additives can be readily incorporated in the hydrogels via hand kneading for potential applications such as soft electronics, bio‐signal sensing, and soft artificial joints.
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This content will become publicly available on July 8, 2025
Strain-Stiffening Mechanoresponse in Dynamic-Covalent Cellulose Hydrogels
Mechanical stimuli such as strain, force, and pressure are pervasive within and beyond the human body. Mechanoresponsive hydrogels have been engineered to undergo changes in their physicochemical or mechanical properties in response to such stimuli. Relevant responses can include strain-stiffening, self-healing, strain-dependent stress relaxation, and shear rate-dependent viscosity. These features are a direct result of dynamic bonds or non- covalent/physical interactions within such hydrogels. The contributions of various types of bonds and intermolecular interactions to these behaviors are important to more fully understand the resulting materials and engineer their mechanoresponsive features. Here, strain-stiffening in carboxymethylcellulose hydrogels crosslinked with pendant dynamic-covalent boronate esters using tannic acid is studied and modulated as a function of polymer concentration, temperature, and effective crosslink density. Furthermore, these materials are found to exhibit self-healing and strain- memory, as well as strain-dependent stress relaxation and shear rate-dependent changes in gel viscosity. These features are attributed to the dynamic nature of the boronate ester crosslinks, inter-chain hydrogen bonding and bundling, or a combination of these two intermolecular interactions. This work provides insight into the interplay of such interactions in the context of mechanoresponsive behaviors, particularly informing the design of hydrogels with tunable strain- stiffening. The multi-responsive and tunable nature of this hydrogel system therefore presents a promising platform for a variety of applications.
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- Award ID(s):
- 1944875
- PAR ID:
- 10577909
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Biomacromolecules
- Volume:
- 25
- Issue:
- 7
- ISSN:
- 1525-7797
- Page Range / eLocation ID:
- 4406 to 4419
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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