Computational design of active, self-reinforcing gels.

Many living organisms have evolved a protective mechanism that allows them to reversibly alter their stiffness in response to mechanical contact. Using theoretical modeling, we design a mechanoresponsive polymer gel that exhibits a similar self-reinforcing behavior. We focus on cross-linked gels that contain Ru(terpy)(2) units, where both terpyridine ligands are grafted to the chains. The Ru(terpy)(2) complex forms additional, chemoresponsive cross-links that break and re-form in response to a repeated oxidation and reduction of the Ru. In our model, the periodic redox variations of the anchored metal ion are generated by the Belousov-Zhabotinsky (BZ) reaction. Our computer simulations reveal that compression of the BZ gel leads to a stiffening of the sample due to an increase in the cross-link density. These findings provide guidelines for designing biomimetic, active coatings that send out a signal when the system is impacted and use this signaling process to initiate the self-protecting behavior.