Deformable and robust core-shell protein microcapsules templated by liquid-liquid phase separated microdroplets

Microcapsules are a key class of microscale materials with applications in areas ranging from personal care to biomedicine, and with increasing potential to act as extracellular matrix (ECM) models of hollow organs or tissues. Such capsules are conventionally generated from non-ECM materials including synthetic polymers. Here, we fabricated robust microcapsules with controllable shell thickness from physically- and enzymatically-crosslinked gelatin and achieved a core-shell architecture by exploiting a liquid-liquid phase separated aqueous dispersed phase system in a one-step microfluidic process. Microfluidic mechanical testing revealed that the mechanical robustness of thicker-shell capsules could be controlled through modulation of the shell thickness. Furthermore, the microcapsules demonstrated environmentally-responsive deformation, including buckling by osmosis and external mechanical forces. A sequential release of cargo species was obtained through the degradation of the capsules. Stability measurements showed the capsules were stable at 37 {\deg}C for more than two weeks. Finally, all-aqueous liquid-liquid phase separated and multiphase liquid-liquid phase separated systems were generated with the gel-sol transition of microgel precursors. These smart capsules are promising models of hollow biostructures, microscale drug carriers, and building blocks or compartments for active soft materials and robots.