High-Efficient Electrochemiluminescence of DNA-Au Ag Nanoclusters with Au NPs@Ti₃C₂ as a Novel Coreaction Accelerator for Ultrasensitive Biosensing

In this work, an ultrasensitive electrochemiluminescence (ECL) biosensor was constructed based on DNA-stabilized Au Ag nanoclusters (DNA-Au Ag NCs) as the efficient luminophore and Au NPs@Ti₃C₂ as a new coreaction accelerator for determining microRNA-221 (miRNA-221) related to liver cancer. Impressively, DNA-Au Ag NCs were stabilized by the high affinity of the periodic 3C sequence, exhibiting an excellent ECL efficiency of 27% compared with classical BSA-Au Ag NCs (16%). Moreover, the Au NPs@Ti₃C₂ nanocomposites, as a new coreaction accelerator, were first introduced to accelerate the production of abundant sulfate free radicals (SO₄^•-) for promoting the ECL efficiency of DNA-Au Ag NCs in the DNA-Au Ag NCs/Au NPs@Ti₃C₂/S₂O₈^2- ternary system due to the energy band of Au NPs@Ti₃C₂ being well-matched with the frontier orbital of S₂O₈^2-. Furthermore, the trace target (miRNA-221) could drive the rolling circle amplification to generate an amount of output DNA with periodic 3C and 10A sequences. Through covalent bonds on the surface of poly A and Au NPs, the distance between the luminophor and the coreaction accelerator could be narrowed to further enhance the detection sensitivity. As a result, the constructed sensor has been applied for the ultrasensitive detection of miRNA-221 with a low detection limit of 50 aM and successfully monitored miRNA-221 in MHCC-97L and HeLa cell lysates. This strategy could be utilized for guiding the synthesis of light-emitting DNA-metal NCs, which has great potential in the construction of ultrasensitive biosensors for the early diagnosis of diseases.