A Comparative Study of Molecularly Imprinted Polypyrrole Architectures for Electrochemical Quartz Microbalance-Based Method Development for Geraniol Adsorption

Molecularly imprinted polymers (MIPs) are widely employed for selective adsorption of target molecules in sensing and separation applications. The architecture of MIP films can influence adsorption behavior, interfacial stability, and reusability, yet systematic investigations of these effects are limited. This study aimed to evaluate how different polypyrrole (PPy) MIP film architectures affect the adsorption, stability, and regeneration characteristics of geraniol-imprinted layers on gold electrodes. Geraniol-imprinted and non-imprinted PPy films were electropolymerized onto quartz crystal microbalance (QCM) substrates. Two film architectures were compared: (i) a single-layer geraniol-imprinted PPy film, and (ii) a double-layer film consisting of a non-imprinted PPy underlayer followed by a geraniol-imprinted layer. Film characterization was performed using cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) measurements. Adsorption–desorption cycles were conducted to assess mass uptake, signal stability, and regeneration performance. EQCM analysis revealed that the double-layer architecture exhibited enhanced frequency signal stability during repeated adsorption–desorption cycles compared to single-layer films, suggesting a stabilizing effect of the underlying non-imprinted PPy layer at the electrode interface. Geraniol-imprinted films demonstrated significantly higher mass uptake than non-imprinted controls, confirming the sensitivity provided by molecular imprinting. Single-layer films showed more variability in signal response and less consistent regeneration performance. The architecture of MIP films significantly affects adsorption behavior, stability, and regeneration on electrode surfaces. Incorporating a non-imprinted PPy underlayer can improve signal reproducibility and enhance the robustness of MIP-based sensing interfaces. These findings provide guidance for the rational design of MIP coatings for electrochemical sensors and QCM-active platforms.