Colorimetric response of fluorescein-modified multilayer thin films induced by electrolysis of water

The surface of an indium-tin oxide (ITO) electrode was coated with layer-by-layer (LbL) thin films composed of fluorescein-modified poly(allylamine) (F-PAH) and poly(styrenesulfonic acid) (PSS) and their UV-visible absorption spectra were recorded under the influence of electrode potential. The LbL films were prepared by an alternate deposition of F-PAH and PSS on the surface of ITO electrode through an electrostatic force of attraction. The intensity of the absorption band around 500 nm originating from fluorescein residues in the LbL film depended on the pH of the solution in which the LbL film is immersed. The intensity of the absorption band decreased when the electrode potential higher than + 1.2 V was applied, while virtually no response was observed at lower electrode potential. The spectral change was suppressed in solutions with higher buffer capacity. The results were discussed in terms of the changes in local pH in the vicinity of the electrode surface, which in turn was induced by electrolysis of H₂O on the electrode surface.