Chemically Fueled Volume Phase Transition of Polyacid Microgels

Microgels are soft colloids that show responsive behavior and are easy to functionalize for applications. They are considered key components for future smart colloidal material systems. However, so far microgel systems have almost exclusively been studied in classical responsive switching settings using external triggers, while internally organized, autonomous control mechanisms as found in supramolecular chemistry and DNA nanotechnology relying on fuel‐driven out‐of‐equilibrium concepts have not been implemented into microgel systems. Here, we introduce chemically fueled transient volume phase transitions (VPTs) for poly(methacrylic acid) (PMAA) microgels, where the collapsed hydrophobic state can be programmed using the fuel concentration in a cyclic reaction network. We discuss details of the system behavior as a function of pH and fuel amount, unravel kinetically trapped regions and showcase transient encapsulation and time‐programmed release as a first application.