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Abstract Hydrogels containing thermosensitive polymers such as poly(N‐isopropylacrylamide) (P(NIPAm)) may contract during heating and show great promise in fields ranging from soft robotics to thermosensitive biosensors. However, these gels often exhibit low stiffness, tensile strength, and mechanical toughness, limiting their applicability. Through copolymerization of P(NIPAm) with poly(Acrylic acid) (P(AAc)) and introduction of ferric ions (Fe3+) that coordinate with functional groups along the P(AAc) chains, here a thermoresponsive hydrogel with enhanced mechanical extensibility, strength, and toughness is introduced. Using both experimentation and constitutive modeling, it is found that increasing the ratio of m(AAc):m(NIPAm) in the prepolymer decreases strength and toughness but improves extensibility. In contrast, increasing Fe3+concentration generally improves strength and toughness with little decrease in extensibility. Due to reversible coordination of the Fe3+bonds, these gels display excellent recovery of mechanical strength during cyclic loading and self‐healing ability. While thermosensitive contraction imbued by the underlying P(NIPAm) decreases slightly with increased Fe3+concentration, the temperature transition range is widened and shifted upward toward that of human body temperature (between 30 and 40 °C), perhaps rendering these gels suitable as in vivo biosensors. Finally, these gels display excellent adsorptive properties with a variety of materials, rendering them possible candidates in adhesive applications.
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Metal Coordination‐Mediated Functional Grading and Self‐Healing in Mussel Byssus Cuticle
Abstract Metal‐containing polymer networks are ubiquitous in biological systems, and their unique structures enable a variety of fascinating biological behaviors. Cuticle of mussel byssal threads, containing Fe‐catecholate complexes, shows remarkably high hardness, high extensibility, and self‐healing capability. Understanding strengthening and self‐healing mechanisms is essential for elucidating animal behaviors and rationally designing mussel‐inspired materials. Here, direct evidence of Fe3+and Fe2+gradient distribution across the cuticle thickness is demonstrated, which shows more Fe2+inside the inner cuticle, to support the hypothesis that the cuticle is a functionally graded material with high stiffness, extensibility, and self‐healing capacity. The mechanical tests of the mussel threads show that both strength and extensibility of the threads decrease with increasing oxygen contents, but this property degradation can be restored upon removing the oxygen. The first‐principles calculations explain the change in iron coordination, which plays a key role in strengthening, degradation, and self‐healing of the polymer networks. The oxygen absorbs on metal ions, weakening the iron‐catecholate bonds in the cuticle and collagen core, but this process can be reversed by sea water. These findings can have important implications in the design of next‐generation bioinspired robust, highly extensible materials, and catalysis.
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- Award ID(s):
- 1662288
- PAR ID:
- 10455463
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Science
- Volume:
- 6
- Issue:
- 23
- ISSN:
- 2198-3844
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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