Ultrasensitive toltrazuril sulfone detection in eggs via a AuNPs/NH2–Ce-MOF-enhanced electrochemical immunosensor

Abstract

The widespread use of toltrazuril (TOL) as a low-toxicity anticoccidial agent in livestock production necessitates sensitive monitoring of its persistent metabolite, toltrazuril sulfone (TOS), which exhibits hepatotoxic and reproductive risks at subchronic exposure levels. Here, we proposed a novel electrochemical immunosensor for the ultrasensitive detection of TOS in eggs, utilizing a decorated amino-functionalized cerium metal–organic framework–gold nanoparticle (NH₂–Ce-MOF/AuNP) nanocomposite. The NH₂–Ce-MOF was synthesized via hydrothermal crystallization of (NH₄)₂Ce(NO₃)₆ and 2-aminoterephthalic acid, exhibiting exceptional stability and an expansive surface area. Compared to conventional electrodes, NH₂–Ce-MOF-modified electrodes promoted AuNP nucleation and provided more active sites for HAuCl₄ deposition, while also enhancing antibody binding, thereby improving the detection sensitivity of electrochemical immunosensors. Subsequently, electrodeposited HAuCl₄ enhanced both electron transfer kinetics (charge transfer resistance decreased by 68% compared to a bare electrode) and bioreceptor loading capacity. Electrochemical evaluation demonstrated superior sensor performance, achieving a wide linear range of 0.05–100 ng mL⁻¹ (R² = 0.998) with an ultralow limit of detection of 33.2 pg mL⁻¹ (S/N = 3), representing a 3-fold improvement over conventional enzyme-linked immunosorbent assays. The electrochemical immunosensor exhibited excellent selectivity and reproducibility (relative standard deviation <10%). This platform establishes a robust foundation for monitoring TOS residues and other hazardous contaminants in complex food matrices.