There is a global debate and concern about the use of glyphosate (Gly) as an herbicide. New toxicological studies will determine its use in the future under new strict conditions or its replacement by alternative synthetic or natural herbicides. In this context, we designed biomimetic polymer sensing layers for the selective molecular recognition of Gly. Towards this end, complementary surface acoustic wave (SAW) and electrochemical sensors were functionalized with polypyrrole (PPy)-imprinted polymer for the selective detection of Gly. Their corresponding limits of detection were on the order of 1 pM, which are among the lowest values ever reported in literature. The relevant dissociation constants between PPy and Gly were estimated at [K_d1 = (0.7 ± 0.3) pM and K_d2 = (1.6 ± 1.4) µM] and [K_d1 = (2.4 ± 0.9) pM and K_d2 = (0.3 ± 0.1) µM] for electrochemical and gravimetric measurements, respectively. Quantum chemical calculations permitted to estimate the interaction energy between Gly and PPy film: ΔE = −145 kJ/mol. Selectivity and competitivity tests were investigated with the most common pesticides. This work conclusively shows that gravimetric and electrochemical results indicate that both MIP-based sensors are perfectly able to detect and distinguish glyphosate without any ambiguity.

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.