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Sensors 2017, 17(11), 2586; https://doi.org/10.3390/s17112586

Highly Selective Polypyrrole MIP-Based Gravimetric and Electrochemical Sensors for Picomolar Detection of Glyphosate

1
Institut National de Recherches et d’Analyses Physico-chimiques, Laboratoire Matériaux, Traitement et Analyse, BiotechPole Sidi-Thabet, 2032 Ariana, Tunisia
2
Unité de Recherche en Modélisation des Sciences Fondamentales et Didactiques, Université de Tunis El Manar, Tunis, Campus Universitaire Farhat-Hached Tunis, Rommana 1068, Tunisia
3
Cnam, SATIE, UMR CNRS 8029, 292 Rue Saint Martin, 75003 Paris, France
4
LAUM, UMR CNRS 6613, Université du Maine, Avenue Olivier Messiaen, 72085 Le Mans CEDEX 9, France
5
ITODYS, UMR CNRS 7086, Université Paris Sorbonne Paris Cité, 15 Rue J-A de Baïf, 75013 Paris, France
6
CNRS, ICMPE, UMR CNRS 7182, 2-8 rue Henri Dunant, 94320 Thiais, France
7
Faculté de Médecine de Monastir, Laboratoire d’Interfaçe et de Matériaux Avancés, Université de Monastir, Av. Avicenne, 5000 Monastir, Tunisia
*
Author to whom correspondence should be addressed.
Received: 6 October 2017 / Revised: 30 October 2017 / Accepted: 7 November 2017 / Published: 9 November 2017
(This article belongs to the Special Issue Surface Acoustic Wave and Bulk Acoustic Wave Sensors)
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Abstract

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 [Kd1 = (0.7 ± 0.3) pM and Kd2 = (1.6 ± 1.4) µM] and [Kd1 = (2.4 ± 0.9) pM and Kd2 = (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. View Full-Text
Keywords: glyphosate; molecularly imprinted polymer (MIP); gravimetric sensor; electrochemical sensor; DFT calculation; dissociation constants glyphosate; molecularly imprinted polymer (MIP); gravimetric sensor; electrochemical sensor; DFT calculation; dissociation constants
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Mazouz, Z.; Rahali, S.; Fourati, N.; Zerrouki, C.; Aloui, N.; Seydou, M.; Yaakoubi, N.; Chehimi, M.M.; Othmane, A.; Kalfat, R. Highly Selective Polypyrrole MIP-Based Gravimetric and Electrochemical Sensors for Picomolar Detection of Glyphosate. Sensors 2017, 17, 2586.

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