Electrochemical molecularly imprinted polymers in microelectrode devices

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Research Letter

Electrochemical molecularly imprinted polymers in microelectrode devices Vitalys Mba Ekomo and Catherine Branger, Laboratoire MAPIEM, EA 4323, Université de Toulon, 83041 Toulon Cedex 9, France Ana-Mihaela Gavrila and Andrei Sarbu, National Research and Development Institute for Chemistry and Petrochemistry ICECHIM, Advanced Polymer Materials and Polymer Recycling, 202 Splaiul Independentei, 060021 Bucharest, Romania Dimitrios A. Koutsouras, Clemens Stolz, and George G. Malliaras, Department of Bioelectronics, Ecole Nationale Supérieure des Mines, CMP-EMSE, MOC, 13541 Gardanne, France Hugues Brisset , Laboratoire MAPIEM, EA 4323, Université de Toulon, 83041 Toulon Cedex 9, France Address all correspondence to Hugues Brisset at [email protected] (Received 4 February 2020; accepted 15 April 2020)

Abstract This work demonstrated the possibility to integrate electrochemical molecularly imprinted polymers (e-MIPs) on microelectrodes to detect organic pollutants. e-MIPs are a cross-linked polymer with specific target binding cavities with a redox tracer inside. e-MIPs were obtained by precipitation copolymerization of ferrocenylmethyl methacrylate as a functional monomer and a redox tracer with ethylene glycol dimethacrylate as a cross-linker and bisphenol A as a target molecule. FTIR and elemental analysis confirmed the presence of ferrocene inside the polymers. Nitrogen adsorption/desorption experiments and binding isotherms demonstrated the presence of binding cavities inside the eMIP. The electrochemical properties of the e-MIP were characterized in organic/aqueous media before their patterned on microelectrode.

Introduction Molecularly Imprinted Polymers (MIPs) are a threedimensional polymer network prepared via a cross-linking step between a functional monomer and a cross-linker around a molecular template. The removal of this template creates specific binding cavities leading to high selective recognition properties, high stability associated with a low cost. Therefore, MIPs can advantageously take place in biosensor devices.[1–3] In this context, MIPs have been quickly integrated in electrochemical sensors as stable recognition elements for the detection of electroactive molecular targets via amperometry, potentiometry, or impedance measurements.[3–6] Conducting polymers have also been widely used to develop electrosynthesized MIPs to detect non-electroactive targets in electrochemical sensors.[7] The main advantage of this way is the easy preparation of welldefined thin MIP films, but the main difficulty is to maintain the binding cavities because of the use of uncross-linked polymers.[8] Recently, some electropolymerizable cross-linkers were tested to prepare three-dimensional electrosynthesized MIPs, and this approach seems to be promising.[9] Since few years, we developed another strategy based on the introduction of a redox probe as a functional comonomer in the cross-linked MIP to design an electrochemical MIP (e-MIP) in order to detect non-electroactive molecular targets.[10–14] Our main obje