Influence of the chemical functionalities of a molecularly imprinted conducting polymer on its sensing properties: electrochemical measurements and semiempirical DFT calculations.
Starting from thiophene-based functional monomers (FM), namely, TMA, TAA, TMeOH, EDOT, and Th, bonded to atrazine (ATZ) target molecules into FM/ATZ prepolymerization dimers in acetonitrile solutions, differently functionalized molecularly imprinted conducting polymers (FM-MICP) are electrosynthesized and then washed and used as sensitive layers for ATZ recognition. Sensitivity of these layers toward ATZ, which is quantified by cyclic voltammetric measurements, decreases in the following order of functional monomers: TMA, TAA, TMeOH, EDOT, and Th. Absolute values of the FM-ATZ dimerization free energies are calculated with the help of DFT/PCM calculations and of an empirical correction of the entropy effects, using a modified Wertz formula. A strong correlation is found between FM-MICP sensitivity and the amount of FM/ATZ prepolymerization complexes.
Laboratoire de Conception de Capteurs Chimiques et Biologiques, LC3B, Conservatoire National des Arts et Métiers, CNAM, 292 rue Saint-Martin, 75141 Paris Cedex 03, France.
Youssef
Y
Lattach
Pierre
P
Archirel
Samy
S
Remita
D001280:Atrazine / Q000032:analysis*; D019281:Dimerization; D055664:Electrochemical Techniques / Q000379:methods; D006540:Herbicides / Q000032:analysis*; D054802:Molecular Imprinting / Q000379:methods; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D013816:Thermodynamics; D013876:Thiophenes / Q000737:chemistry*
D006540:Herbicides; D011108:Polymers; D013876:Thiophenes; D001280:Atrazine