Advancing green chemistry for the sensitive and selective detection of N-nitrosodiethylamine (NDEA) monitoring: the role of nanomaterial-embedded electropolymerized molecularly imprinted polymer-based sensors

Abstract

N-Nitrosodiethylamine (NDEA), a potent carcinogen with an acceptable intake (AI) of 26.5 ng/day, poses a significant health risk, necessitating accurate detection and quantification. Here, we introduce the first-ever molecularly imprinted polymer (MIP)-based electrochemical sensor, NDEA/ZnONPs@APTES/CHT/3-TBA@MIP/GCE, for the selective and sensitive detection of NDEA. The sensor was fabricated by depositing green-synthesized 3-aminopropyl triethoxysilane (APTES)-functionalized ZnO nanoparticles (ZnONPs) onto a glassy carbon electrode (GCE), followed by electropolymerization (EP) with chitosan (CHT) and 3-thienyl boronic acid (3-TBA) to form a molecularly imprinted polymeric film. The APTES-ZnONPs were characterized using IR and Raman spectroscopies, XRD, zeta-size, and -potential analyses, while the polymeric films, synthesized with and without NDEA, were analyzed via SEM. Electrochemical characterization was performed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) by using 5.0 mM [Fe(CN)6]3-/4- solution as a redox probe for quantitative detection of NDEA. The developed sensor exhibited high selectivity and sensitivity for NDEA over a concentration range of 0.1-1.0 pM, achieving detection and quantification Limits of 5.92 fM and 19.80 fM in standard solutions and 12.60 fM and 42.00 fM in commercial serum samples, respectively. It maintained high recovery percentages even in biological interferents, potential impurities such as N-nitrosodimethylamine (NDMA), and drug substances like sartans, demonstrating exceptional selectivity. Furthermore, a Green Analytical Chemistry (GAC) assessment classified the sensor as an environmentally superior alternative to traditional methods, achieving a 99% greener score. This pioneering green MIP-based sensor presents a promising platform for environmental monitoring, portable and miniaturized sensing, and rapid on-site NDEA detection, addressing the urgent need for sensitive, selective, and eco-friendly analytical tools.