Spatio‐Temporal Processes of Diffusion‐Controlled Communication in Hierarchical Multi‐Compartments

Abstract Exploring the synergy of feedback behavior and molecular communication between micro‐ and nanocompartments is of great implication for the development of advanced hierarchical living‐like materials. Non‐covalent interactions are the driving forces for dynamic and temporal events in biomimetic structures. Herein, pH‐responsive hierarchical multi‐compartments (HMC) are constructed via hydrophobic–hydrophobic interactions between azobenzene units and phospholipid layers through the integration of two distinct structural units: phospholipid‐membranized coacervates (Coa@DMPC) and azobenzene‐functionalized polymersomes (Azo‐Psomes). This enables us to study spatio‐temporal signal pathways for biomimetic pH homeostasis and the triggering of feedback‐controlled peroxidase‐like behavior of Azo‐Psomes within HMC. Compared with undocking systems, the information transmission process within HMC shows a high efficiency. Besides the continuous addition of nutrients, the synchronization of two different biomimetic reactions in HMC requires the spatial loading of glucose oxidase and L‐phenylalanine ammonia lyase in coacervates and of L‐phenylalanine or beta‐cyclodextrin/hemin complexes in Azo‐Psomes. Azo‐Psomes exhibit pH‐responsive feedback‐controlled behavior. The pH‐responsive membrane of Azo‐Psomes is responsible for the spatio‐temporal peroxidase‐like activity of lumen‐integrated beta‐cyclodextrin/hemin complexes in Azo‐Psomes. Finally, this strategy provides a new approach for constructing more complex biomimetic systems by interconnecting at least two membrane‐containing compartments to further explore the synergistic mechanisms and feedback behaviors among artificial cell communities.