AgInZnS quantum dots as anodic emitters with strong and stable electrochemiluminescence for biosensing application

Quantum dots (QDs) have become promising electrochemiluminescence (ECL) emitters with high quantum yield and size-tunable luminescence. However, most QDs generate strong ECL emission at the cathode, developing anodic ECL-emitting QDs with excellent performance is challenging. In this work, low-toxic quaternary AgInZnS QDs synthesized by a one-step aqueous phase method were used as novel anodic ECL emitters. AgInZnS QDs exhibited strong and stable ECL emission and a low excitation potential, which could avoid the side reaction of oxygen evolution. Furthermore, AgInZnS QDs displayed high ECL efficiency (Φ_ECL) of 5.84, taking the Φ_ECL of Ru(bpy)₃²⁺/tripropylamine (TPrA) ECL system as 1. Compared to AgInS₂ QDs without Zn doping and traditional anode luminescent CdTe QDs, the ECL intensity of AgInZnS QDs was 1.62 times and 3.64 times higher than that of AgInS₂ QDs and CdTe QDs, respectively. As a proof-of-concept, we further designed an "on-off-on" ECL biosensor for detecting microRNA-141 based on a dual isothermal enzyme-free strand displacement reaction (SDR), which not only to achieve the cyclic amplification of the target and ECL signal, but also to construct a switch of the biosensor. The ECL biosensor had a wide linear range from 100 aM to 10 nM with a low detection limit of 33.3 aM. Together, the constructed ECL sensing platform is a promising tool for rapid and accurate diagnosis of clinical diseases.