A new molecularly imprinted electrochemical sensor was proposed to determine 4,4'-methylene diphenyl diamine (MDA) using molecularly imprinted polymer-multiwalled carbon nanotubes modified glassy carbon electrode (MIP/MWCNTs/GCE). GCE was coated by MWCNTs (MWCNTs/GCE) because of their antifouling qualities and in order to improve the sensor sensitivity. To make the whole sensor, a polymeric film made up of chitosan nanoparticles was electrodeposited by the cyclic voltammetry method on the surface of MWCNTs/GCE in the presence of MDA as a template. Different parameters such as scan cycles, elution time, incubation time, molar ratio of template molecules to functional monomers, and pH were optimized to increase the performance of the MIP sensor. With a detection limit of 15 nM, a linear response to MDA was seen in the concentration range of 0.5-100 µM. The imprinting factor (IF) of the proposed sensor was also calculated at around 3.66, demonstrating the extremely high recognition performance of a MIP/MWCNT-modified electrode. Moreover, the sensor exhibited good reproducibility and selectivity. Finally, the proposed sensor was efficiently used to determine MDA in real samples with satisfactory recoveries ranging from 94.10% to 106.76%.
Keywords: 4,4′-methylene diphenyl diamine; chitosan; electrochemical sensor; molecularly imprinted polymer; primary aromatic amine.