Selectivity and Efficiency of Conductive Molecularly Imprinted Polymer (c-MIP) Based on 5-Phenyl-Dipyrromethane and 5-Phenol-Dipyrromethane for Quorum Sensing Precursors Detection

Functional polymers that selectively recognize target compounds are developed by imprinting polymerization. In the present paper, two different dipyrromethanes, 5-phenoldipyrromethane (5-pOH-DP) and 5-phenyl-dipyrromethane (5-ph-DP), are synthetized and investigated to develop conductive molecularly imprinted polymer (cMIP) sensors. As target molecules, two homoserine lactone derivatives were templated by an electrochemically driven polymerization process. Acyl-homoserine lactones (AHLs), also called homoserine lactones (HS), are a class of signaling molecules involved in bacterial quorum sensing (QS), which is a strategy of coordination among bacteria mediated by population density. The preparation of cMIP from 5-pOH-DP and 5-ph-DP in the presence of acetyl-homoserine lactone (Acetyl-HS) or carboxybenzyl-homoserine lactone (Cbz-HS) was performed by cyclic voltammetry (CV). The cMIP selectivity and sensitivity were assessed by microgravimetry (QCM). Both series of measurements were performed with the aid of an Electrochemical Quartz Crystal Microbalance (EQCM/QCM). The experimental evidences are discussed with respect to NMR measurements that were conducted to gain insight into the interactions established between monomers and templates. The NMR data interpretation offers preliminary information about the most probable positions involved in interaction development for both molecules and highlights the role of the hydration shell. The QCM-cMIP sensor was able to detect the analyte in the linear range from 10−8 mol·L−1 to 10−6 mol·L−1 and a limit of detection (LOD) of 22.3 ng (3σ of the blank signal) were evaluated. QCM rebinding tests demonstrated that cMIP selectivity was driven by the pendant group of dipyrromethane, which was also confirmed by the NMR data.