Biomimetic strain-stiffening in fully synthetic dynamic-covalent hydrogel networks
Rachel C. Ollier, Yuanhui Xiang, Adriana M. Yacovelli, Matthew J. Webber
Abstract
dynamic-covalent boronate ester crosslinks. Shear rheology reveals the strain-stiffening response in these networks as a function of polymer concentration, pH, and temperature. Across all three of these variables, hydrogels of lower stiffness exhibit higher degrees of stiffening, as quantified by the stiffening index. The reversibility and self-healing nature of this strain-stiffening response is also evident upon strain-cycling. The mechanism underlying this unusual stiffening response is attributed to a combination of entropic and enthalpic elasticity in these crosslink-dominant networks, contrasting with natural biopolymers that primarily strain-stiffen due to a strain-induced reduction in conformational entropy of entangled fibrillar structures. This work thus offers key insights into crosslink-driven strain-stiffening in dynamic-covalent phenylboronic acid-diol hydrogels as a function of experimental and environmental parameters. Moreover, the biomimetic mechano- and chemoresponsive nature of this simple ideal-network hydrogel offers a promising platform for future applications.