Approaches for regulated fluid secretion, which typically rely on fluid encapsulation and release from a shelled compartment, do not usually allow for a fine, continuous modulation of secretion, and can be difficult to adapt for monitoring or functionintegration purposes. 1-5 Here, we report self-regulated, self-reporting secretion systems consisting of liquid-storage compartments in a supramolecular polymer-gel matrix with a thin liquid layer on top, and demonstrate that dynamic liquid exchange between the compartments, matrix and surface layer allows for repeated, responsive self-lubrication of the surface layer and for cooperative healing of the matrix. Depletion of the surface liquid or local material damage induces self-regulated secretion of the stored liquid via a dynamic feedback between polymer crosslinking, droplet shrinkage and liquid transport that can be read out through changes in the system's optical transparency. We envision diverse applications in fluid delivery, wetting and adhesion control, and material self-repair.Nearly every form of living tissue autonomously packages, transports, and secretes fluids, mediating defense, adhesion, wound healing, temperature -often several of these at once -through tightly self-regulated release systems. [6][7][8][9] Fundamental to these systems, fluid storage is itself an active, finely regulated balance. Storage droplets or vesicles continuously adjust their size, shape and contents through ongoing exchange with the surroundings, creating intrinsically responsive control mechanisms that tie secretion to a wide range of chemical and physical stimuli and feedback signals. [10][11][12][13] At the same time, collective changes in the stores are reported to the organism, alerting it that it needs to drink or eat to replenish the limited supply. Many synthetic approaches have been developed to enable triggered release from microcapsules, hydrogels, nanoparticles, vesicles, micelles, mesoporous carriers and other containers. [1][2][3][4][5][14][15][16][17] While these systems can secrete fluid in response to various stimuli, it remains a challenge to design a synthetic approach that displays finely tuned, continuous self-adjustment, integrated functionalities, and continuous liquid supply monitoring.2 Figure 1. Schematic of the self-regulated, liquid secretion system. Secretion liquid is stored as shell-less droplets inside a gel matrix composed of dynamic polymers, with ongoing liquid exchange between droplet and gel phases. If S = γ ga -(γ la + γ gl ) > 0, the matrix surface will be coated with a thin liquid overlayer. When this layer is removed, the disjoining pressure will trigger secretion of the stored liquid to restore the original film thickness, while the supramolecular gel matrix reconfigures through reversible bond disassembly and reassembly to release any buildup of mechanical stress due to shrinking droplets. With successive removal/restoring cycles, the liquid droplets will continuously shrink and the gel will become progressively transparent.Inspire...
