Pesticides are among the most important contaminants in food, leading to important global health problems. While conventional techniques such as high-performance liquid chromatography (HPLC) and mass spectrometry (MS) have traditionally been utilized for the detection of such food contaminants, they are relatively expensive, time-consuming and labor intensive, limiting their use for point-of-care (POC) applications. Electrochemical (bio)sensors are emerging devices meeting such expectations, since they represent reliable, simple, cheap, portable, selective and easy to use analytical tools that can be used outside the laboratories by non-specialized personnel. Screen-printed electrodes (SPEs) stand out from the variety of transducers used in electrochemical (bio)sensing because of their small size, high integration, low cost and ability to measure in few microliters of sample. In this context, in this review article, we summarize and discuss about the use of SPEs as analytical tools in the development of (bio)sensors for pesticides of interest for food control. Finally, aspects related to the analytical performance of the developed (bio)sensors together with prospects for future improvements are discussed.
A direct competitive immunosensor for the electrochemical determination of Imidacloprid (IMD) pesticide on gold nanoparticle-modified screen-printed carbon electrodes (AuNP-SPCE) is here reported for the first time. Self-obtained specific monoclonal antibodies are immobilized on the AuNP-SPCE taking advantage of the AuNPs biofunctionalization abilities. In our biosensor design, free IMD in the sample competes with IMD conjugated with horseradish peroxidase (IMD-HRP) for the recognition by the antibodies. After that, 3,3′,5,5′-Tetramethylbenzidine (TMB) is enzymatically oxidized by HRP, followed by the oxidized TMB reduction back at the surface of the SPCE. This process gives an associated catalytic current (analytical signal) that is inversely proportional to the IMD amount. The main parameters affecting the analytical signal have been optimized, reaching a good precision (repeatability with a RSD of 6%), accuracy (relative error of 6%), stability (up to one month), selectivity and an excellent limit of detection (LOD of 22 pmol L -1 ), below the maximum levels allowed by the legislation, with a wide response range (50 -10000 pmol L -1 ). The detection through antibodies also allows to have an excellent selectivity against other pesticides potentially present in real samples. Low matrix effects were found when analysisng IMD in tap water and watermelon samples. The electrochemical immunosensor was also validated with HPLC-MS/MS, the reference method used in official laboratories for IMD analysis, through statistical tests. Our findings make the electrochemical immunosensor as an outstanding method for the rapid and sensitive determination of IMD at the point-of-use.
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