The development of preconcentration methods in the design of electrochemical sensors is attractive due to the lack of efficient strategy for the preconcentration of organic analytes. Herein, we described the employment of electropolymerization as a novel preconcentration approach in the electrochemical de- termination of melamine (Mel). In this effort, the preconcentration of Mel occurred at a glassy carbon electrode modified with overoxidized Poly-(para–aminophenol) film (GCE/Ox-PPAP) using the potentiody- namic technique. In fact, non-electroactive Mel was electrochemically converted into electroactive poly- (melamine) (PMel) during the electrochemical preconcentration step. The preconcentrated Mel was quan- tified using the square wave voltammetry (SWV), as the electro-analytical signal. The electrochemical preconcentration step was studied using cyclic voltammetry (CV), computer simulation, electrochemi- cal impedance spectroscopy (EIS), and field emission scanning electron microscope (FESEM) techniques. GCE/Ox-PPAP revealed a good calibration sensitivity of 4.718 μ A L μ mol −1 in the linear range of 2.0 to 60 μ mol L −1 , and a limit of detection (LOD) of 0.34 μmol L −1 (S/N = 3). The obtained LOD is lower than the safety limit of Mel in milk and dairy products. Moreover, in this work, the electropolymerization process as the electrochemical preconcentration approach leads to the selective determination of Mel in the presence of possible interferences. Finally, the developed method was successfully used for the Mel detection in real milk samples. The obtained results will also open up opportunities for the design of novel electroanalytical method using a simple strategy.
