Near-infrared electrochemiluminescence biosensors facilitated by thermally activated delayed fluorescence (TADF) emitters for ctDNA analysis

Abstract

The near-infrared electrochemiluminescence technique (NIR ECL) has gained significant attention as a powerful analytical tool in biomedicine and clinical diagnosis due to its inherent advantages. In this work, we successfully synthesized a novel NIR ECL emitter of TPA-DCPP nanoparticles (NPs) with a D-π-A-π-D configuration. By utilizing the thermally activated delayed fluorescence (TADF) property, we achieved enhanced electrochemiluminescence (ECL) emission through complete exciton harvesting for radiative decay. Specifically, when BDEA was used as a co-reactant, the TPA-DCPP NPs exhibited strong bandgap ECL emission. Additionally, they demonstrated an exceptionally higher ECL efficiency compared to conventional near-infrared fluorescence organic nanomaterials (BSeT-BT NPs). By integrating the efficient anodic ECL performance of TPA-DCPP NPs with Exo III-assisted polymerase enzyme reaction cascade amplification, a highly efficient ECL resonance energy transfer (ECL-RET) platform was developed for ultrasensitive detection of circulating tumor DNA (ctDNA). The established biosensor demonstrated an exceptional linear dynamic range and achieved attomolar-level detection limit. This study highlights the immense potential of TADF emitters in enhancing ECL efficiency and extends the emission wavelength of organic nanomaterials to the NIR region, thereby expanding their applications in biological analysis.

Keywords: Circulating tumor DNA; ECL biosensor; ECL resonance energy transfer; Near-infrared electrochemiluminescence; Thermally activated delayed fluorescence.