This study reports a new chemical sensor based on ion-imprinted polymer matrix using copper nanoparticles-polyaniline nanocomposite (IIP-Cu-NPs/PANI). This sensor was prepared by electropolymerization using aniline as a functional monomer and nitrate as template onto the copper nanoparticles-modified glassy carbon (GC) electrode surface. Both ion-imprinted (IIP) and nonimprinted (NIP) electrochemical sensor surfaces were evaluated using UV-Visible spectrometry and scanning electron microscopy (SEM). The electrochemical analysis was made via cyclic voltammetry (CV), linear sweep voltammetry (LSV), and impedance spectroscopy (IS). Throughout this study various analytical parameters, such as scan rate, pH value, concentration of monomer and template, and electropolymerization cycles, were optimized. Under the optimum conditions, the peaks current of nitrate was linear to its concentration in the range of 1μM-0.1M with a detection limit of 31μM and 5μM by EIS and LSV. The developed imprinted nitrate sensor was successfully applied for nitrate determination in different real water samples with acceptable recovery rates.
A shear horizontal surface acoustic wave sensor (SH-SAW) operating at 104 MHz was functionalized with a polypyrrole (PPy) molecularly imprinted polymer (MIP) for selective detection of flumequine (FLU) in aqueous media. In order to prevent the formation of FLU complexes with the gold sensing area of the SH-SAW sensor, a thin blocking polypyrrole layer was deposited by chronoamperometry before the MIP electrochemical deposition. The detection limit of the designed sensor was of the order of 1 μM and the sensitivity was estimated to be at 9.36 ± 0.39° mM−1. Selectivity tests were made with levofloxacin (LEVO), an interfering fluoroquinolone antibiotic. Results indicate that the designed PPy-MIP recognition layer is selective of flumequine. Quantum chemical calculations, based on density functional theory (DFT), have permitted us to highlight the importance of the PPy blocking layer, on the one hand, and the nature of interactions between the polypyrrole matrix and FLU and LEVO analytes, on the other hand.
This review critically summarizes the knowledge of imprinted polymer-based electrochemical sensors for the detection of pesticides, metal ions and waterborne pathogenic bacteria, focusing on the last five years. MIP-based electrochemical sensors exhibit low limits of detection (LOD), high selectivity, high sensitivity and low cost. We put the emphasis on the design of imprinted polymers and their composites and coatings by radical polymerization, oxidative polymerization of conjugated monomers or sol-gel chemistry. Whilst most imprinted polymers are used in conjunction with differential pulse or square wave voltammetry for sensing organics and metal ions, electrochemical impedance spectroscopy (EIS) appears as the chief technique for detecting bacteria or their corresponding proteins. Interestingly, bacteria could also be probed via their quorum sensing signaling molecules or flagella proteins. If much has been developed in the past decade with glassy carbon or gold electrodes, it is clear that carbon paste electrodes of imprinted polymers are more and more investigated due to their versatility. Shortlisted case studies were critically reviewed and discussed; clearly, a plethora of tricky strategies of designing selective electrochemical sensors are offered to “Imprinters”. We anticipate that this review will be of interest to experts and newcomers in the field who are paying time and effort combining electrochemical sensors with MIP technology.