β-cyclodextrin imprinted film embedded with methylene blue: A host-guest sensitive electrochemical strategy for PFAS detection

Abstract

Per- and polyfluoroalkyl substances (PFAS) have raised significant concerns; however, their accurate detection in aqueous environments remains a major challenge. In this study, a host-guest molecularly imprinted polymer-based electrochemical sensor with enhanced antifouling properties were developed using β-cyclodextrin embedded with methylene blue (βCD-MB MIP). This sensor demonstrated sensitive and selective quantification of perfluorooctanoic acid (PFOA) in real water samples. The βCD-MB MIP was fabricated by electro-polymerizing βCD and MB in the presence of the target molecule, PFOA, where βCD served as the functional monomer and MB as the signaling probe. The incorporation of βCD endowed the MIP with a stable hydration layer, promoting hydrophilicity and inhibiting fouling, while ensuring effective electron transfer from MB, resulting in significant current responses and outstanding antifouling performance. This sensor exhibits excellent sensing capabilities towards PFOA with a detection limit of 1.57 pg mL−1, covering a wide concentration range from 4.14 ng mL−1 to 41.4 mg mL−1. It also displayed high selectivity for PFOA with an imprint factor of 6.5, which is five to seven times higher than that of other perfluorinated analogs. This study introduces an innovative platform for the rapid quantification of PFAS using redox-active MIPs and sets the groundwork for developing integrated sensors for continuous PFAS monitoring in water.