Mechanical switching of a comblike dual dynamic polymer network

Hydrogels are polymer networks swollen in water and, therefore, suitable for biomedical applications. For this purpose, hydrogels have to mimic the functionality and mechanics of natural tissues. In drug delivery, for example, the diffusion is crucial and can be controlled through targeted variation of the network mesh-size. In tissue engineering, on the other side, the mechanics plays a fundamental role and can be strengthened through the use of two interpenetrated polymer networks, realizing a double network, or with two dynamic motifs anchored in one common network, realizing a dual dynamic network (DDN). However, current knowledge encompasses mainly nonlinear rheological characterization of these networks. We intend to fill this gap and provide a systematic linear rheological study. To realize this strategy, we combine two supramolecular motifs in a common network, thereby realizing a comblike DDN with the ability to change the building blocks on demand. In our DDN, a tetra-poly(ethylene) glycol (pEG) (the first building block) is functionalized on each arm with two dynamic motifs: terpyridine capable of undergoing metal-complexation with different divalent metal ions, and a thermo-responsive unit consisting of poly(N-isopropylacrylamide) (pNIPAAm) (the second building block) that is capable of undergoing temperature-dependent nano-phase-separation. In particular, we change the molar mass of the tetra-pEG-terpyridine and the pNIPAAm grafted chains. In addition, we investigate two different metal ions that form complexes with the terpyridine. With this platform, we tune the elastic properties on demand, and we systematically study the structure–property relationships with oscillatory shear rheology in the linear regime.