The functional versatility and endurable self-healing capacity of soft materials in nature is found to originate from the dynamic supramolecular scaffolds assembled via reversible interactions. To mimic this strategy, extensive efforts have been made to design polymer networks with transient crosslinks, which lays the foundation for synthetic self-healing hydrogels. Towards the development of stronger and faster self-healing hydrogels, understanding and controlling the gel network dynamics is of critical importance. since it provides design principles for key properties such as dynamic mechanics and self-healing performance. For this purpose, a universal strategy independent of exact crosslinking chemistry would be regulating the polymer material's dynamic behavior by optimal network design, yet current understanding of the relationship between network structure and macroscopic dynamic mechanics is still limited, and implementation of complex network structure has always been challenging.

In this thesis, we show how the dynamic mechanical properties in a hydrogel can be controlled by rational design of polymer network structures. Using mussel-inspired reversible catechol coordination chemistry, we developed a nanocomposite hydrogel network (NP gel) with hierarchical assembly ofpolymer chains on iron oxide (Fe304) nanoparticles as network crosslinks. With NP gel as a model system, we first investigated its unique dynamic mechanics in comparison with traditional permanent and dynamic gels, and discovered a general approach to manipulate the network dynamics by controlling the crosslink structural functionality. Then we further explored the underlying relationship between polymer network structure and two key parameters in relaxation mechanics, which elucidated universal approaches for designing relaxation patterns in supramolecular transient gel network. Finally, by utilizing these design principles, we designed a hybrid gel network using two crosslinking structures with distinct relaxation timescales. By simply adjusting the ratio of two crosslinks, we can precisely tune the material's dynamic mechanics from a viscoelastic fluid to a rigid solid. Such controllability in dynamic mechanics enabled performance optimization towards mechanically rigid and fast self-healing hydrogel materials. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu).