A Novel Carbon Quantum Dots Signal Amplification Strategy Coupled with Sandwich Electrochemiluminescence Immunosensor for the Detection of CA15-3 in Human Serum

Abstract

A sensitive sandwich electrochemiluminescence immunosensor was established by employing graphene oxide-PEI-carbon quantum dots (CQDs)-Au nanohybrid as probe to measure carbohydrate antigen 15-3 (CA15-3), a breast cancer biomarker. In this work, nanocomposites of Ag nanoparticles and polydopamine (AgNPs-PDA) were synthesized by redox reaction between dopamine and Ag⁺. The nanocomposite with high surface area can provide an efficient substrate for immobilizing initial antibody (Ab1). Carbon quantum dots (CQDs) are fixed on polyethylenimine-functionalized graphene oxide (PEI-GO) by amide bonds. Au nanoparticles are modified on CQDs-decorated PEI-GO substrates. The secondary antibody (Ab2) was immobilized by AuNPs/CQDs-PEI-GO composite. CQDs can be assembled onto the surface of an electrode by incorporation of CA15-3 with Ab1 and Ab2. Under the synergistic action of AgNPs, polydopamine, AuNPs, and PEI-GO, the ECL signal of CQDs is greatly amplified as an excellent conductive material to facilitate electron transfer rate and further increase electrochemical detection capability. Under optimal conditions, the fabricated immunosensor showed a linear concentration range from 0.005 to 500 U mL^-1, with a detection limit of 0.0017 U mL^-1 (signal-to-noise ratio of 3) for CA15-3. The designed ECL immunosensor displayed receivable accuracy, excellent stability, and high specificity. The results of the detection of human serum samples are satisfactory, revealing that the method offers a potential application for the clinical diagnosis of tumor markers.