Engineering mechanical dissipation in solid poly(ethylene glycol) hydrogels with bio-inspired metal-coordinate crosslinks

Abstract

Growing evidence supports that the unique mechanical behavior of mussel byssal threads, such as high toughness and self-healing, rely on an intricate balance of permanent covalent and reversible metal coordination bonds. Inspired by this material crosslink chemistry balance, we synthesized polyethylene glycol (PEG) hydrogels with two crosslinked networks; a primary permanent network composed of covalently crosslinked 4-arm PEG and a secondary network composed of 4-arm PEG functionalized with histidine on each arm. The histidine decorated PEG forms a mechanically reversible network via metal ion coordinated crosslinks. Using rheometry, we study the contribution of the metal-coordinate network to the bulk gels mechanics and find that we can control both the amplitude and the frequency of peak mechanical dissipation with the histidine: metal ion ratio and the choice of metal ion, respectively. Furthermore, we can control the mechanical contribution of metal coordinate bonds by changes in pH. These simple bio-inspired gels promise to serve as a new model system for further study of opto-mechanical coupling of metal-coordinate soft materials.