Electrochemical synthesis of phosphorus and sulfur co-doped graphene quantum dots as efficient electrochemiluminescent immunomarkers for monitoring okadaic acid

In this study, water-dispersed, uniform-sized phosphorus and sulfur co-doped graphene quantum dots (P, S-GQDs) were prepared by the one-step electrolysis of a graphite rod in an alkaline solution containing sodium phytate and sodium sulfide. Compared with GQDs and mono-doped GQDs (P-GQDs and S-GQDs), the P, S-GQDs dramatically improved the electrochemiluminescence (ECL) performance. Therefore, they were used as bright ECL signaling markers through conjugation with a monoclonal antibody against okadaic acid (anti-OA-MAb). Moreover, as an effective matrix for OA immobilization, the carboxylated multiwall carbon nanotubes-poly (diallyldimethylammonium) chloride-Au nanocluster (CMCNT-PDDA-AuNCs) composite promoted electron transfer and enlarged the surface area. Owing to the multiple amplifications, a competitive indirect ECL immunosensor for highly sensitive quantitation of OA has been developed. Under the optimized conditions, the 50% inhibitory concentration (IC50) of the immunosensor was 0.25 ng mL(-1), and its linear range was 0.01-20 ng mL(-1) with a low detection limit of 0.005 ng mL(-1). Finally, the proposed ECL sensor was successfully utilized to detect OA contents in mussel samples. Therefore, this study provides new insights into the designation of ECL luminophores and expands application of co-doped GQDs in fabrication of ECL immunosensors for shellfish toxin determination.