Stable and Prolonged Autonomous Oscillation in a Self-Oscillating Polymer Brush Prepared on a Porous Glass Substrate

We developed an autonomous functional surface, named a "self-oscillating polymer brush surface", which exhibits swelling-deswelling of the modified polymer chains synchronized with the Belousov-Zhabotinsky (BZ) reaction. The grafted polymer chain is a random copolymer composed of thermoresponsive N-isopropylacrylamide, N-(3-aminopropyl)methacrylamide, and ruthenium tris(2,2'-bipyridine) [Ru(bpy)₃]. To provide stable oscillations over a long period of time, suppression of the dilution of the BZ reactants inside the polymer surface and the increase in the amount of immobilized Ru(bpy)₃ are important. Here, we modified the self-oscillating polymer brush on a porous glass substrate and characterized its dynamic behavior. The increased surface area of the porous glass allowed for an efficient introduction of the metal catalyst, which resulted in a stable BZ reaction observable by optical microscopy. Compared with an aqueous BZ solution and the self-oscillating polymer modified on a glass coverslip, the wave velocity and diffusion coefficient were significantly lower for the porous glass system, which suggested that the reaction-diffusion of the reactants was markedly different than those of the other two systems. Moreover, the wave velocity was unchanged on the porous glass system for 1 h, whereas that of the solution dropped by 30 μm s^-1. Waveform analyses based on the Field-Körös-Noyes mechanism revealed that densely packed Ru(bpy)₃ in the porous glass system affects the duration of the key processes in the BZ reaction. These findings can help with understanding the dynamic behavior of the self-oscillating polymer brush on a porous glass substrate. Stable self-oscillations on the polymer brush-grafted porous glass substrate will aid future applications such as mass transport systems.