Polyfluorene-Enhanced Near-Infrared Electrochemiluminescence of Heptamethine Cyanine Dye for Coreactants-Free Bioanalysis

The near-infrared electrochemiluminescence (NIR-ECL) technique has received special attention in cell imaging and biomedical analysis due to its deep tissue penetration, low background interference, and high sensitivity. Although cyanine-based dyes are promising NIR-ECL luminophores, limited ECL efficiency and the need for exogenous coreactants have prevented their widespread application. In this work, poly[9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene]-alt-2,7-(9,9-dioctylfluorene)] (PFN) was innovatively developed to significantly invigorate the NIR-ECL performance of heptamethine cyanine dye IR 783 by the resonance energy transfer (RET) strategy. Astonishingly, the IR@PFN nanoparticles (NPs) synthesized from IR 783 and PFN by a nanoprecipitation method emitted a strong coreactant-free NIR-ECL signal at +1.05 V, and the maximum emission wavelength was 815 nm. IR@PFN NPs were integrated in a spontaneous entropy-driven chain replacement (ESDR) reaction to achieve ECL analysis of microRNA-21 (miRNA-21), and the limit of detection was as low as 0.25 fM. IR@PFN NPs created a promising coreactant-free NIR-ECL platform for bioanalysis and imaging, providing a novel NIR-ECL detection method for miRNA-21.