Acompetitive electrochemiluminescence (ECL) immunosensor isproposed to accurately and rapidly assess okadaic acid (OA) levels in shellfish using a novel self-reinforced solid-state ECL marker, which is essential for ensuring seafood safety. Graphene quantum dots doped with nitrogen and sulfur (N,S-GQDs) were synthesized, for the first time, through the electrolysis of graphite in 3-(N-morpholine) propane sulfonic acid solution. Intriguingly, these N,S-GQDs exhibited exceptional co-reactant properties, significantly enhancing the anodic ECL performance of Ru(bpy)32+ in a phosphate-buffered saline solution. Following the functionalization of Ru(bpy)32+-doped silica nanoparticles (RuSiNPs) with poly(diallyldimethylammonium) chloride, we achieved a well-dispersed assembly of N,S-GQDs on the exterior of the RuSiNPs through electrostatic interactions. Importantly, the core-shell structure of RuSiNPs@N,S-GQDs efficiently encapsulated both the luminophore and co-reactant, thus improving the transfer rates of electrons, shorting interaction distances, and reducing energy loss during light emission. Leveraging this "bright" ECL beacon, theECL immunosensor demonstrated remarkable analytical performance, yielding a low half maximal inhibitory concentration (IC50) of 0.14ngmL-1, an extensive linear range spanning 0.003-40ngmL-1, and impressively low limit of detection of 0.001ngmL-1 for OA determination.
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