Microgels are soft colloids that showr esponsive behavior and are easy to functionalizef or applications.T hey are considered key components for future smart colloidal material systems.H owever,s of ar microgel systems have almost exclusively been studied in classical responsive switching settings using external triggers,w hile internally organized, autonomous control mechanisms as found in supramolecular chemistry and DNAn anotechnology relying on fuel-driven out-of-equilibrium concepts have not been implemented into microgel systems.H ere,w ei ntroduce chemically fueled transient volume phase transitions (VPTs) for poly(methacrylic acid) (PMAA) microgels,w here the collapsed hydrophobic state can be programmed using the fuel concentration in ac yclic reaction network. We discuss details of the system behavior as af unction of pH and fuel amount, unravel kinetically trapped regions and showcase transient encapsulation and time-programmed release as afirst application.

In chemically fueled supramolecular materials, molecular self‐assembly is coupled to a fuel‐driven chemical reaction cycle. The fuel‐dependence makes the material dynamic and endows it with exciting properties like adaptivity and autonomy. In contrast to the large work on the self‐assembly of small molecules, we herein designed a diblock copolymer, which self‐assembles into transient micelles when coupled to a fuel‐driven chemical reaction cycle. Moreover, we used these transient block copolymer micelles to locally increase the concentration of hydrophobic reagents and thereby function as a transient nanoreactor.

Out-of-equilibrium phase transitions driven by dissipation of chemical energy are a common mechanism for morphological organization and temporal programming in biology. Inspired by this, dissipative self-assembly utilizes chemical reaction networks...

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.

In chemically fueled supramolecular materials, molecular self-assembly is coupled to a fuel-driven chemical reaction cycle. The fuel-dependence makes the material dynamic and endows it with exciting properties like adaptivity and autonomy. In contrast to the large work on the self-assembly of small molecules, we herein designed a diblock copolymer, which self assembles into transient micelles when coupled to a fuel-driven chemical reaction cycle. Moreover, we used these transient block copolymer micelles to locally increase the concentration of hydrophobic reagents and thereby function as a transient nanoreactor.