Highly Luminescent and Self-Enhanced Electrochemiluminescence of Tris(bipyridine) Ruthenium(II) Nanohybrid and Its Sensing Application for Label-Free Detection of MicroRNA

Inspired by the coreactive activity of carbon nanodots (CDs) and branched polyethylenimine (BPEI) toward electrochemiluminescence (ECL) of Ru­(bpy)₃²⁺, a highly luminescent and self-enhanced ECL nanohybrid (Ru-BCDs) was synthesized through covalently linking BPEI-coated carbon dots (BCDs) with Tris (4,4′-dicarboxylic acid-2,2′-bipyridyl) ruthenium­(II) dichloride (Ru­(dcbpy)₃²⁺). The composition and morphological characterization demonstrated that the spherical Ru-BCDs particles with 12.1 ± 1.4 nm diameter were obtained. The enhanced ECL property of Ru-BCDs was proved to originate from the dual coreactive contribution of BPEI and CDs as coreactants as well as the intramolecular electron transfer process, which could shorten the electron transfer path and minimize energy loss. A carbon nitride nanosheet (CNN) was utilized to stabilize the Ru-BCDs-modified glassy carbon electrode, which greatly improved the stability of solid-state ECL. By utilizing the affinity discrepancy of the CNN to single-stranded and double-stranded nucleic acids, a label-free and signal-on ECL biosensor was constructed for the determination of microRNA-133a (miR-133a), a potential biomarker of acute myocardial infarction. The designed biosensor exhibited good performance of miR-133a detection with a detection limit of 60 fM and could be used for the detection of real human serum with satisfactory results. The self-enhanced ECL nanohybrid with distinguished ECL efficiency holds a promising prospect in biosensing and bioimaging applications.