Abstract
Silica-modified electrodes possess physicochemical properties that make them valuable in electrochemical sensing and energy-related applications. Although intrinsically insulating, silica thin films can selectively interact with redox species, producing sieving effects that enhance electrochemical responses. We synthesized Class I hybrid silica matrices incorporating either negatively charged poly(4-styrene sulfonic acid) or positively charged poly(diallyl dimethylammonium chloride). These hybrid films were deposited onto ITO electrodes and evaluated via cyclic voltammetry in aqueous ferrocenium solutions. The polyelectrolyte charge played a key role in the electroassisted incorporation of ferrocene: silica-PSS films promoted accumulation, while silica-PDADMAC films hindered it due to electrostatic repulsion. In situ UV-vis spectroscopy confirmed that only a fraction of the embedded ferrocene was electroactive. Nevertheless, this fraction enabled effective mediated detection of cytochrome c in solution. These findings highlight the crucial role of ionic interactions and hybrid composition in electron transfer to redox proteins, providing valuable insights for the development of advanced bioelectronic sensors.