Signal-Enhanced Immunosensor-Based MOF-Derived ZrO2 Nanomaterials as Electrochemiluminescence Emitter for D-Dimer Detection.

Abstract

Metal oxide nanomaterials have garnered significant attention in the field of electrochemiluminescence (ECL) sensing due to their efficient, stable, and nontoxic properties. However, the current research on metal oxide nanomaterials has primarily focused on their cathodic luminescence properties, with limited reports on their anodic ECL properties. In this study, we utilized MOF-derived ZrO2 nanomaterials as luminophores to generate stable anodic ECL signals in the presence of the coreactant tripropylamine (TPrA). Additionally, a signal-enhancing immunosensor was developed to analyze D-dimer by incorporating the coreaction accelerator Cu-doped TiO2 (TiO2-Cu). The ZrO2 synthesized by calcining UiO-67 demonstrated nontoxicity and biocompatibility, exhibiting efficient and stable ECL emission in a TPrA solution. The inclusion of TiO2-Cu as a coreaction accelerator in the immunosensor resulted in the formation of a ternary system of ZrO2/TiO2-Cu/TPrA. The Cu doping effectively narrowed the bandgap of TiO2 and enhanced its conductivity. As a substrate, TiO2-Cu reacted with more TPrA, generating sufficient free radicals to effectively enhance the ECL signal of ZrO2. In this article, a short peptide ligand, NFC (NARKFYKGC), was designed to immobilize antibodies and maintain the activity of antigen-binding sites during the construction of the immunosensor. The developed immunosensor was used for the accurate detection of D-dimers, with a wide linear range of 0.05-600 ng/mL and a low detection limit of 21 pg/mL..