Reconfiguration of Multiphase Coacervate Droplets Into Self‐Regulated Nested Artificial Cells

Dynamic sub‐compartmentalization and internal organization are important assets of living cells to control functional complexity. Mimicking these features in artificial cells provides a platform to effectively respond to external cues by changing internal structure, thereby emulating life‐like behavior. Here, we present a strategy to construct sub‐compartmentalized artificial cells by converting multiphase coacervate droplets (MCDs) into nested coacervate vesicles (NCVs), in which the outer host domain is electrostatically reconfigured into a continuous semipermeable shell, while the internal guest droplets are preserved. The generated artificial cells exhibit spatial segregation of coacervate constituents and encapsulated fluorescent dyes, enzymes, and gold nanoparticles, and remain morphologically stable under different conditions. The membranized artificial cells display artificial metabolic features by means of poly(N‐isopropylacrylamide) (PNIPAAm) synthesis and subsequent temperature‐dependent aggregation, leading to emergent behavior including self‐regulated photothermal transitions, feedback‐mediated photocatalysis, and spatiotemporal organization of internal cargoes. Overall, our approach establishes a robust artificial cell platform that combines sub‐compartmentalization with self‐regulating properties, integrating functionality with structural complexity.