MIP-MEPS based sensing strategy for the selective assay of dimethoate. Application to wheat flour samples

The aim of this work was to demonstrate the potentialities of the use of a molecularly imprinted (MIP) sensor coupled to a microextraction by packed sorbent (MEPS) strategy for the selective and sensitive detection of dimethoate in real samples. A dimethoate-polypyrrole MIP film was realised by cyclic voltammetry (CV) on the surface of a glassy carbon electrode (GCE). Being dimethoate electro-inactive, K₃[Fe(CN)₆] was used as probe for the indirect quantification of the analyte via the decrease of redox peaks observed upon binding of the target analyte. Detection of dimethoate at low nanomolar range was achieved with linearity in the 0.1-1nM range. Relative standard deviation calculated for different electrodes at 0.5nM of dimethoate was < 3% and selectivity was very satisfactory being the response for omethoate only 23% of dimethoate. A MEPS strategy for the extraction of dimethoate from a challenging matrix as wheat flour was then used in conjunction with the MIP electrochemical sensor. The procedure applied to flour samples spiked with dimethoate at 0.5 MRL, MRL, and 1.5 MRL gave very favourable comparison with a validated UHPLC-MS/MS method with deviations in the -21% /+17% range, demonstrating the feasibility of the approach as screening assay. This work clearly shows that the sequential use of a microextraction based procedure and electrochemical sensing system is low cost, easy to realise and use and can open new perspectives for the development of selective sensing system to be used in field or decentralised lab testing for the selective screening of target analytes.