Developing a generally applicable electrochemical sensor for detecting macrolides in water with thiophene-based molecularly imprinted polymers

Our screening data revealed the threat macrolide antibiotics, especially azithromycin (AZN), posed to human health with its increasing occurrence in water environment. The electrochemical sensor based on molecularly imprinted polymer (MIP) is a promising platform that caters for the next generation of intelligent wastewater treatment plants (WWTPs) by virtue of its wide tolerance to water from all sources and in-situ monitoring. However, low initiation potentials of cross-linking monomers contributed by the electron-rich circumstance allowed them to usurp sites designed for functional monomers when electrically stimulated, leading to an unsatisfactory binding capacity. Another uncertainty is that multiple reaction sites of cross-linking monomers granted them complex polymerization routes and made it difficult to ensure the consistency of preparation. Serval monomers had been investigated with electrochemical tools and the performance of sensors constructed with these monomers were compared in this study. Based on the results, we proposed a protocol in which a novel functional monomer possessing a stronger electron-donating group, phenyl, was adopted to compete for the dominance in electropolymerization. Beyond that, the cross-linking monomer was modified with electron-withdrawing groups to raise its initiation potential. A monothiophene with a moderate initiation potential was also recruited as the linker to address the steric hindrance. In this way, polymerization proceeded in a specific order. It is worth mentioning that the Marangoni flow is an ideal tool to deal with the Coffee-ring deposition while drop-casting. The resulting sensor showed good performance with a limitation of detection (LOD) of 0.120 μM for AZN and a satisfactory selectivity, and the design can be applied to constructing sensors for a variety of macrolide antibiotics.