A novel dual signal and label-free electrochemical aptasensor for mucin 1 based on hemin/graphene@PdPtNPs

A dual signal and label-free electrochemical aptasensor for mucin 1 was constructed based on hemin/graphene@PdPtNPs nanocomposite (H-Gr@PdPtNPs). Hemin attached on the graphene surface not only improves the solubility of graphene and acts as an in-situ electrochemical probe but also exhibits excellent peroxidase-like properties to electrocatalyze the reduction of H₂O₂. PdPtNPs also show outstanding catalytic capacity to the reduction of H₂O₂ and provide numerous binding sites for loading dDNA (mucin 1 aptamer and cDNA) to form the sensing interface. In the presence of mucin 1, due to the specific affinity between aptamer and mucin 1, double helix would be induced dissociation and the aptamer would be pulled off from the electrode. As a result, the electrochemical signals of hemin and H₂O₂ were recovered. Based on these properties, the label-free and sensitive dual signal electrochemical biosensor for mucin 1 detection has been developed. The one is differential pulse voltammetry (DPV) signal of hemin and the other is chronoamperometry signal arisen from the catalytic reduction of H₂O₂. The linear ranges for mucin 1 were 8.0 pg mL^-1 to 80 ng mL^-1 and 0.8 pg mL^-1 to 80 ng mL^-1 with the limit of detection 2.5 pg mL^-1 and 0.25 pg mL^-1 by DPV and chronoamperometry, respectively. The recovery of mucin 1 in human blood serum samples was from 95.0% to 104.2%. The detection platform does not need signal labeling which greatly reduced the sophisticated and expensive procedures. The aptasensor provide a promising strategy for the determination of mucin 1 in clinical diagnostics.