Aspects of the Belousov-Zhabotinsky Reaction inside a Self-Oscillating Polymer Brush

We have developed a novel polymer brush surface exhibiting autonomous swelling-deswelling changes driven by the Belousov-Zhabotinsky (BZ) reaction, that is, the self-oscillating polymer brush. In this system, the ruthenium tris(2,2'-bipyridine) [Ru(bpy)₃] catalyst-conjugated polymer chains are densely packed on the solid substrate. It is expected that the BZ reaction in the polymer brush would be influenced by the immobilization effect of the catalyst. To clarify the effect of the immobilization of the catalyst on the self-oscillating polymer brush, the self-oscillating behavior of the polymer brush was investigated by comparing it with that of other self-oscillating polymer materials, the free polymer, and the gel particle under various initial substrate concentrations. The initial substrate dependency of the oscillating period for the polymer brush was found to be different from those for the free polymer and the gel particle. Furthermore, the oscillatory waveform was analyzed on the basis of the Field-Körös-Noyes model. These investigations revealed that the dense immobilization of the self-oscillating polymer on the surface restricted accessibility for the Ru(bpy)₃ moiety. These findings would be helpful in understanding the reaction-diffusion mechanism in the polymer brush, which is a novel reaction medium for the BZ reaction.