Abstract
In recent years, stimuli-responsive hydrogels have gained tremendous interest in designing complex smart 4D materials for applications ranging from biomedicine to soft electronics that can change their properties on demand over time. However, at present, a hydrogel's response is often induced by merely a single stimulus, restricting its broader applicability. The controlled hierarchical assembly of various hydrogel building blocks, each with a tailored set of mechanical and physicochemical properties as well as programmed stimulus response, may potentially enable the design and fabrication of multi-responsive polymer parts that process complex operations, like signal routing dependent on different stimuli. Since inter-connection stability of such building blocks directly accompanies the transmission of information across building blocks and is as important as the building property itself to create complex 4D materials, we provide a study on the utility of an inter-crosslinking mechanism based on UV-induced 2,3-dimethylmaleimide (DMMI) dimerization to inter-connect acrylamide-based and N-isopropylacrylamide-based millimeter-sized cubic building blocks, respectively. The resulting dual-crosslinked assemblies are freestanding and stable against contraction-expansion cycles in solution. In addition, the approach is also applicable for connecting microfluidically fabricated, micrometer-sized hydrogel spheres, with the resulting assemblies being processable and mechanical stable, likewise resisting contraction-expansion in different solvents, for instance.