Chemically-fueled phase transition of a redox-responsive polymer

In living systems, dynamic biomacromolecular assemblies are driven and regulated by energy dissipative chemical reaction networks, enabling various autonomous functions. Inspired by this biological principle, we report a chemically-fueled phase transition of a poly(<i>N</i>-isopropylacrylamide) (PNIPAAm)-based polymer bearing viologen units (P(NIPAAm-V)), wherein redox changes drive coil-to-globule phase transitions. Upon the addition of a reducing agent, viologen moieties in P(NIPAAm-V) are converted into their reduced state, resulting in enhanced hydrophobicity and polymer aggregation. Coexistence of a platinum catalyst couples these redox-driven structural changes to hydrogen evolution, which oxidizes the viologen radicals, thus restoring the polymer chains to their hydrated random coil state. As a result, transient polymer assemblies form and subsequently disassemble upon depletion of the reducing agent, leading to a temporally controlled out-of-equilibrium phase transition. Moreover, by tuning the platinum concentration and reaction temperature, we achieve precise control of both the size and lifetime of these assemblies. Notably, viologen moieties constitute only about 1% of the polymer repeating units, underscoring that chemically-fueled phase transition is efficient strategy for dynamically regulating molecular assemblies. These findings demonstrate that chemically-fueled phase transitions in redox-responsive polymers offer a promising blueprint for designing dynamic, biomimetic materials capable of spatiotemporally regulated structural transformations.