Autonomous and Communicative Microcapsule Systems for Life‐Like Homeostatic pH Regulation

ABSTRACT Life sustains complex functions through intercellular communication networks that coordinate collective behavior and regulate environmental homeostasis. Replicating such dynamic and autonomous control over extended spatial and temporal domains in synthetic materials remains significant challenges. Here, we present a programmable dual‐microcapsule system that emulates life‐like homeostatic pH regulation via an antagonistic enzymatic network. The system integrates urease microcapsules (UMCs) and esterase microcapsules (EMCs), which were produced using microfluidic devices coupled with a surface co‐assembly strategy. By integrating hybrid junction geometry with a modified epoxy post‐coating strategy, the 3D‐printed microfluidic device overcomes intrinsic structural defects and surface irregularities. The resulting amphiphobic and defect‐free channels ensure stable droplet production and precise microsphere fabrication. Individual capsules display pH‐mediated negative feedback through adaptive shell permeability, whereas mixed populations display communicate behaviors via pH signaling to generate programmable pH oscillations and feedback‐controlled pH stabilization. This platform exhibits robust reaction to external pH control, long‐term cycling stability, and inter‐capsule interaction. This work offers a versatile route for engineering communicative, autonomous, and adaptive material systems, with broad implications for biomedical devices, environmental regulation, and soft control using chemical information exchange.