Compartmentalized Dynamic Supramolecular Hydrogels through Chemically Fueled Self‐Assembly in Aqueous Two‐Phase Systems

Compartmentalized dynamic supramolecular structures are prevalent in living systems and underpin numerous pivotal biological functions, yet their recapitulation in synthetic scenarios remains largely underexplored. Here, we report on compartmentalized supramolecular hydrogels that can dynamically evolve their structure and properties through chemically fueled self‐assembly in aqueous two‐phase systems (ATPSs) and uncover an unexpected dynamic interactive behavior between the hydrogel networks and ATPSs. By chemically fueling the self‐assembly of a simple peptide‐based gelator throughout aqueous emulsions of two immiscible polymer solutions, compartmentalized supramolecular hydrogel networks are generated. With the fuel dissipation, these hydrogels spontaneously disintegrate over time, with tunable lifetime and regeneration capacity. Interestingly, during the fueling process, the gelators are covalently decorated by one of the polymers in the ATPS, imparting the resultant hydrogel network with homotypic affinity for the corresponding polymer phase. This affinity drives an unexpected migration of the polymer phase, reminiscent of the migration of living cells assisted by the extracellular matrix. In turn, we leverage the polymer‐decorated gelator to control the compartmentalization regions of the hydrogel networks. This work would accelerate the exploitation of new supramolecular materials with lifelike features, including compartmentalized architectures, self‐evolving capacity, and interactive behaviors.