Selective apigenin assay in plant extracts and herbal supplement with molecularly imprinted polymer-based electrochemical sensor

This study is the first successful application of a nanomaterial-supported molecularly imprinted polymer (MIP)-based electrochemical sensor for the sensitive and selective determination of apigenin (API), which is a naturally occurring product of the flavone class that is an aglycone of several glycosides. Secondary metabolites are biologically active substances produced by plants in response to various environmental factors. The levels of these compounds can vary depending on factors such as climate, soil conditions and the season in which the plants are grown. Therefore, the analysis of these compounds is essential to properly understand the biological effects of plant extracts and to ensure their safe use. To increase the glassy carbon electrode (GCE) surface's active surface area and porosity, zinc oxide nanoparticles (ZnO NPs) were integrated into the MIP-based electrochemical sensor design. Tryptophan methacrylate (TrpMA) was selected as the functional monomer along with other MIP components such as 2-hydroxyethyl methacrylate (HEMA, basic monomer), 2-hydroxy-2-methylpropiophenone (initiator), and ethylene glycol dimethacrylate (EGDMA, crosslinking agent). The morphological and electrochemical characterizations of the developed API/ZnO NPs/TrpMA@MIP-GCE sensor were performed with scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The indirect measurement approach via 5.0 mM [Fe(CN)₆]^3–/4– solution was utilized to determine API in the linear range of 1.0x10⁻¹³ M − 1.0x10⁻¹² M. The limit of detection (LOD) and limit of quantification (LOQ) for standard solutions were found to be 2.47x10⁻¹⁴ and 8.23x10⁻¹⁴ M, respectively. In addition, the extraction processes were carried out using ultrasound-assisted extraction (UAE) and maceration (MCR) procedures. For Apium graveolens L., Petroselinum crispum (Mill.) Fuss and herbal supplement, the API recoveries varied from 98.79 % to 102.71 %, with average relative standard deviations (RSD) less than 2.25 % in all three cases. The sensor's successful performance in the presence of components with chemical structures similar to the API was also demonstrated, revealing its unique selectivity.