Surface-Defect-Involved and Eye-Visible Electrochemiluminescence of Unary Copper Nanoclusters for Immunoassay

A single-stabilizer-capped strategy is proposed for achieving highly efficient and surface-defect-involved electrochemiluminescence (ECL) from unary copper nanoclusters (NCs) via employing l-cysteine (Cys) as a capping agent of luminophore. The Cys-capped CuNCs (Cys-CuNCs) can be electrochemically injected with valence band (VB) holes and exhibit eye-touchable ECL processes around +0.95 and +1.15 V upon employing TPrA as a coreactant. Both accumulated ECL spectra and spooling ECL spectra demonstrated that the two ECL processes are of the same single waveband and spectrally identical to each other with the same maximum emission wavelength of 640 nm. Promisingly, ECL of the Cys-CuNCs/TPrA system is obviously red-shifted for ∼150 nm to PL of Cys-CuNCs, indicating that the bandgap-engineered routes for ECLs of Cys-CuNCs are completely blocked. The oxidative-reduction ECL process of the Cys-CuNCs/TPrA system is a kind of highly efficient, eye-visible, and single-color emission in surface-defect-involved route. The capping agent of Cys can enable the CuNCs/TPrA system with a stronger ECL than other thiol capping agents, so that Cys-CuNCs are utilized as ECL tags for sensitive and selective immunoassays, which exhibit a wide linear response range from 0.05 pg/mL to 0.5 ng/mL and a limit of detection of 0.01 pg/mL (S/N = 3) with carcinoembryonic antigen as the analyte. Moreover, both the luminophore Cys-CuNCs and conjugates Ab₂-CuNCs can be safely stored in aqueous media without any protector, which is promising for the evolution and clinic application of metal NC ECL in the surface-defect-involved route.