Beginning: November 2018
Defence: October 3rd, 2022
Supervisors: BRANGER Catherine, BRISSET Hugues, MARGAILLAN André
PhD defense on October 3rd 2022
The use of copper as a biocide in anti-fouling coatings on ships has led to its accumulation in harbour waters. The aim of this work is to develop electrochemical sensors for its detection in marine samples. For this purpose, copper(II)-imprinted polymers were prepared and used for the modification of electrodes.
Firstly, imprinted polymer particles were synthesised using a cross-linking agent (ethylene glycol dimethacrylate or N,N’-methylene-bis-acrylamide) and a functional monomer, methacrylamido-L-histidine (MAH), which can form a complex with copper(II). The physico-chemical characterization of the polymer particles confirmed the integration of MAH and allowed to evaluate the morphological properties of the polymers.
The copper(II) binding properties were then evaluated and the particles with the best performance were used to make carbon paste electrodes. These electrodes, with a detection limit of 5.9 x 10-2 µM (or 3.75 µg/L), allowed the determination of copper(II) in marine samples.
Finally, new approaches for surface modification were explored for in situ polymer film formation. Thus, iniferters were grafted onto gold electrodes by the formation of self-assembled monolayers but also by electropolymerisation of a polymer with pendant iniferter functions. The latter route allowed the photopolymerisation of a copper(II)-imprinted polymer film on a carbon electrode.
Imprinted polymers, electrochemistry, copper, surface modification, iniferter, electropolymerisation