Cross-Hierarchical Analysis of Self-Oscillating Polymer Materials Through Activation Energy.

In chemically driven soft materials, polymer architecture can shape how chemical reactions are transduced into material-level dynamic behavior. However, the relationship between polymer architecture and the resulting dynamics remains insufficiently understood. Here, using Arrhenius analysis, we perform a cross-hierarchical comparison of the temperature dependence of Belousov-Zhabotinsky (BZ) reaction-driven oscillatory dynamics across three structurally related systems: molecular Ru(bpy)3Cl2, a linear self-oscillating polymer (SOP), and a self-oscillating microgel (SOMG). In these systems, Ru(bpy)3 complex is present in solution as a molecular catalyst or covalently incorporated into either a linear polymer or a crosslinked microgel network. The resulting apparent activation energies Ea, app are used to quantify the overall temperature dependence of their oscillatory dynamics. In the SOP, the redox and coacervation/dissolution oscillations exhibit similar Ea, app values, indicating that periodic liquid-liquid phase separation had only a limited effect on the overall temperature dependence. In contrast, in the SOMG, the flocculation/dispersion oscillation exhibits a substantially higher Ea, app than the redox oscillation. Moreover, the relative order of Ea, app between the SOP and SOMG is reversed between the redox and structural oscillatory modes. These results indicate that Ea, app is modulated by both the underlying polymer architecture and the architecture-dependent structural dynamics accompanying BZ-driven oscillations.