AuPt NPs with enhanced electrochemical oxidization activity for ratiometric electrochemical aptasensor

Strong and stable electrochemical beacons are critical for the achievement of sensitive and reliable electroanalysis applications. In this work, the electrochemical oxidation performance of AuPt NPs was studied and firstly found to be largely enhanced under light illumination. Plasmonic AuPt NPs collected light energy after local surface plasmon resonance (LSPR) excitation and generated much more holes to participate in the electrochemical oxidation process of Pt⁰ in AuPt NPs. AuPt NPs with the electrochemical oxidation peak at around -0.7 V were utilized as detection probes for the fabrication of ratiometric electrochemical aptasensor, by introducing Co-MOF/Fe₃O₄/Ag nanosheets (NSs) with the electrochemical oxidation peak at 0.1 V as reference beacons. The aptamers of epithelial cell adhesion molecule (EpCAM) modified AuPt NPs were assembled with Co-MOF/Fe₃O₄/Ag NSs, which generated strong detection and reference signals at -0.7 V and 0.1 V, respectively. The high affinity between EpCAM and aptamers induced the separation of AuPt NPs from Co-MOF/Fe₃O₄/Ag NSs, resulting in the decrease of detection signal at -0.7 V and unchanged reference signal at 0.1 V. A ratiometric electrochemical aptasensor was achieved for the sensitive and reliable quantification of EpCAM in the range from 100 pg/mL to 100 ng/mL. The limit of detection (LOD) was calculated to be 13.8 pg/mL for EpCAM. Plasmon-driven electrochemical oxidation enhancement principle provides the possibility for the design and fabrication of more strong and anti-interference electroactive plasmonic metal-Pt composite nanostructures for the electroanalysis applications.