A novel triple templates molecularly imprinted biosensor assisted by first derivatives of second-order hydrodynamic differential normal pulse voltametric data and multi-way calibration methods for simultaneous biosensing of penicillin, tetracycline and amoxicillin in dairy products: A novel multi-disciplinary study

In this work, a screen printed carbon electrode (SPCE) was used as a platform to fabricate a novel electrochemical biosensor assisted by the first derivatives of the second-order hydrodynamic differential normal pulse voltammetric (HDNPV) data modeled by multivariate curve resolution alternating least squares (MCR-ALS) and parallel factor analysis applied to shift invariant amplitude spectra (PARASIAS) for simultaneous determination of penicillin (PC), tetracycline (TC), and amoxicillin (AC) in dairy products. The SPCE was modified with poly(3,4-ethylenedioxythiophene) (PEDOT) by electropolymerization of the EDOT. Triple templates molecularly imprinted polymers (TTMIPs) were synthesized by using acrylic acid as the functional monomer, and TC, PC, and AC as the template molecules, and epichlorohydrin as a crosslinking agent. The TTMIPs were mixed with multi-walled carbon nanotubes-graphene-ionic liquid (MWCNTs-GR-IL), and drop-casted onto the surface of PEDOT/SPCE. The first derivatives of individual HDNPV responses of the TTMIPs-MWCNTs-GR-IL/PEDOT/SPCE to TC, PC and AC were univariately calibrated, and their linear ranges were used to develop second-order calibration models using MCR-ALS and PARASIAS whose performances were validated by application of them to a validation set with the aim of choosing the best model to assist the biosensor for the analysis of yogurt, milk, and yogurt drink as real samples. The biosensor assisted by MCR-ALS showed a better performance than PARASIAS which forced us to make a final decision on choosing it to assist the biosensor for the analysis of real matrices. The methodology developed in this work was benefited from TTMIIPs, good structure of the biosensor, and three-way calibration models which helped us to develop a novel electroanalytical method for simultaneous determination of TC (0.1–9 pM), PC (1–10 pM), and AC (0.35–8 pM) whose performance in analysing real matrices was comparable with the HPLC-UV as the reference method.