Near-Infrared Electrogenerated Chemiluminescence from Simple Copper Nanoclusters for Sensitive Alpha-Fetoprotein Sensing

Exploiting low cost, water-soluble, and near-infrared (NIR) emissive electrochemiluminophores (ECLphores) is significantly important for biological applications. In this study, bright and NIR electrogenerated chemiluminescence (ECL) emissive copper nanoclusters (Cu NCs) were synthesized through a facile one-pot wet chemical reduction method. ECL properties of obtained Cu NCs were examined in the presence of potassium persulfate, resulting in maximum intensity at 735 nm, at least 135 nm red-shifted with respect to all other Cu NCs. Electrochemistry, photoluminescence (PL), and spooling ECL spectroscopies were used to track NIR ECL emission of Cu NCs ascribed to the monomeric excited states. Due to the abundant binding sites of bovine serum albumin (BSA) to anchor target biomolecules, a sandwich-type ECL immunosensor was thus fabricated using such BSA-templated Cu NCs as tags and alpha fetoprotein antigen (AFP) as a model protein for the first time. Without assisting any signal amplification strategies, the proposed NIR ECL biosensor exhibited a wide linear range (1-400 ng mL(-1)) and low detection limit (0.02 ng mL(-1)) as well as superior selectivity and reproducibility and was successfully applied in real human serum sample determination. This work sets the stage for the development of novel non-noble metal nanoclusters for large-scale and emerging nanotechnology applications.