Hybrid Mn Atomic Clusters/Single-Dispersed Atoms with Dual Antioxidant Activities for a Chemiluminescent Immunoassay

Single-dispersed atoms (SDAs) as catalysts have drawn extensive attention due to their ultimate atom utilization efficiency and desirable catalytic capability. Atomic clusters (ACs) with potential multiple enzyme-like activities also display great practicability in catalysis-based biosensing. In this work, hybrid Mn ACs/SDAs were implanted in the frameworks of defect-engineered MIL 101(Cr) modulated by excess acetic acid, with a high loading capability of 13.9 wt %. Distinctively, Mn SDAs display weak superoxide dismutase (SOD)-like activity for specifically eliminating superoxide anion (O2•-), while Mn ACs/SDAs display both catalase-like and SOD-like activities for remarkable elimination of total reactive oxygen species (ROS) due to the cooperative effect of the two atom-scale catalytic sites. Thus, Mn ACs/SDAs can efficiently inhibit the chemiluminescent (CL) emission of multiple ROS-mediated luminol systems with a superior quenching rate of 85.5%. To validate the practicability of Mn ACs/SDAs for a sensitive CL assay, an immunoassay method was established to detect acetamiprid by using Mn ACs/SDAs as signal quenchers, which displayed a quantification range of 10 pg mL-1-25 ng mL-1 and a detection limit of 3.3 pg mL-1. This study paves an avenue for developing ACs/SDAs with multiple antioxidant activities that are suitable for application in biosensing.