Copper-Doped Terbium Luminescent Metal Organic Framework as an Emitter and a Co-reaction Promoter for Amplified Electrochemiluminescence Immunoassay

This work designed a signal amplification strategy for construction of a highly sensitive electrochemiluminescence (ECL) biosensor by doping Cu²⁺ in a terbium luminescent metal organic framework (Cu:Tb-MOF) to act as a co-reaction promoter, which enhanced the generation of SO₄^•- radical during the cathodic process in the presence of K₂S₂O₈ as a co-reactant. The porous and hollow morphology and the size of Cu:Tb-MOF could be efficiently tuned via changing the molar ratio of Cu²⁺ and Tb³⁺ and the reaction time, which were related to the specific surface area, pore diameter, and the ECL intensity of the MOF structure. To further improve the sensitivity of the ECL biosensor, H₂O₂ was introduced into the ECL system to act as another co-reaction promoter, leading to a new ECL mechanism involving dual co-reaction promoters. In view of the low electron transfer resistance of Cu:Tb-MOF, a label-free ECL immunosensor was conveniently constructed by co-immobilizing Cu:Tb-MOF and the capture antibody on the electrode surface. Using pro-gastrin-releasing peptide (ProGRP, a biomarker of small-cell lung cancer) as the model target, the proposed immunosensor exhibited excellent performance with a detection range of 1.0 pg·mL^-1 to 50 ng·mL^-1 and a limit of detection down to 0.68 pg·mL^-1 (3σ). This work demonstrated a strategy to use the MOF structures as both an emitter and a co-reaction promoter for amplified ECL emission and proposed an innovative route to extend the application of lanthanide MOFs.