Peptide-Based Biosensor with a Luminescent Copper-Based Metal-Organic Framework as an Electrochemiluminescence...

A copper-based metal-organic framework (JUC-1000) has emerged as a promising electrochemiluminescence (ECL) emitter in the domains of bioanalysis and immunoassay. Herein, a highly efficient signal "on-off" peptide-based biosensor was constructed for trypsin (TPN) assay. JUC-1000 synthesized using an organic ligand of H₄BDPO was functionalized as the ECL emitter, whose cathodic ECL behavior in aqueous media was first investigated using potassium persulfate (K₂S₂O₈) as the coreactant. To further amplify the ECL signal, highly catalytic Ag@CeO₂ nanoparticles were fabricated as both a substrate and an coreaction accelerator, which can efficiently catalyze the reduction of S₂O₈^2- to generate more sulfate anion radicals (SO₄^•-) for ECL enhancement, thereby generating strong and stable ECL signals in a "signal on" state. The functionalized JUC-1000 emitter was connected to the Ag@CeO₂ sensing layer though a heptapeptide (HWRGWVC, HGC), and TPN as the target can specifically cleave the carboxyl side of arginine residues in HGC, leading to the release of emitters in a "signal off" state. Based on the efficient signal-switching, the biosensor exhibited linear ECL responses to the added TPN concentration, realizing sensitive detection of TPN in 10 fg/mL to 100 ng/mL with a limit of detection of 3.46 fg/mL. This work proposed an attractive orientation for the fundamental research of applying transition metal-organic frameworks as ECL emitters in bioanalysis and immunoassay.