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Electrochemosensor for Trace Analysis of Perfluorooctanesulfonate in Water Based on a Molecularly Imprinted Poly(o-phenylenediamine) Polymer

  • Najmeh Karimian
    Najmeh Karimian
    Department of Molecular Sciences and Nanosystems, University Ca’ Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
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  • , 
  • Angela M. Stortini
    Angela M. Stortini
    Department of Molecular Sciences and Nanosystems, University Ca’ Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
    More by Angela M. Stortini
  • , 
  • Ligia M. Moretto
    Ligia M. Moretto
    Department of Molecular Sciences and Nanosystems, University Ca’ Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
    More by Ligia M. Moretto
  • , 
  • Claudio Costantino
    Claudio Costantino
    Department of Molecular Sciences and Nanosystems, University Ca’ Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
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  • , 
  • Sara Bogialli
    Sara Bogialli
    Department of Chemical Sciences, University of Padova, via F. Marzolo 1, 35131 Padova, Italy
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    Orcidhttp://orcid.org/0000-0002-9152-3602
  • , and 
  • Paolo Ugo*
    Paolo Ugo
    Department of Molecular Sciences and Nanosystems, University Ca’ Foscari of Venice, via Torino 155, 30172 Venezia Mestre, Italy
    *E-mail: [email protected]
    More by Paolo Ugo
    Orcidhttp://orcid.org/0000-0003-4803-4755
Cite this: ACS Sens. 2018, 3, 7, 1291–1298
Publication Date (Web):June 18, 2018
https://doi.org/10.1021/acssensors.8b00154
Copyright © 2018 American Chemical Society
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    Abstract

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    This work is aimed at developing an electrochemical sensor for the sensitive and selective detection of trace levels of perfluorooctanesulfonate (PFOS) in water. Contamination of waters by perfluorinated alkyl substances (PFAS) is a problem of global concern due to their suspected toxicity and ability to bioaccumulate. PFOS is the perfluorinated compound of major concern, as it has the lowest suggested control concentrations. The sensor reported here is based on a gold electrode modified with a thin coating of a molecularly imprinted polymer (MIP), prepared by anodic electropolymerization of o-phenylenediamine (o-PD) in the presence of PFOS as the template. Activation of the sensor is achieved by template removal with suitable a solvent mixture. Voltammetry, a quartz crystal microbalance, scanning electron microscopy and elemental analysis were used to monitor the electropolymerization process, template removal, and binding of the analyte. Ferrocenecarboxylic acid (FcCOOH) has been exploited as an electrochemical probe able to generate analytically useful voltammetric signals by competing for the binding sites with PFOS, as the latter is not electroactive. The sensor has a low detection limit (0.04 nM), a satisfactory selectivity, and is reproducible and repeatable, giving analytical results in good agreement with those obtained by HPLC-MS/MS analyses.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssensors.8b00154.

    • Optical characterization of MIP sensor; EQCM monitoring of electropolymerization; Profilometric measurement; Comparison between redox probes; Optimization of conditions for MIPs/AuE preparation (PDF)

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