Spatial-Resolved Photoelectrochemical Biosensing Array Based on a CdS@g-C3N4 Heterojunction: A Universal Immunosensing Platform for Accurate Detection.

The detection of biomarkers with high sensitivity and accuracy in real biosamples remains challenging. Herein, a universal spatial-resolved photoelectrochemical (PEC) ratiometry for biodetection of prostate-specific antigen (PSA) as model biomarker was designed for the first time based on a dual-electrode array modified by CdS@g-C3N4 heterojunction coupled with CuS quantum dots (QDs) as signal amplification tags. Specifically, a new kind of photoactive material, the CdS@g-C3N4 p-n heterojunction with high photoelectric conversion efficiency and good chemical stability, was synthesized and immobilized on two spatial-resolved electrodes (WE1 and WE2). After immobilizing gold nanoparticles and capturing PSA antibodies on the electrodes, WE1 incubated with various concentrations of PSA was taken as a working electrode, whereas WE2 with a fixed concentration of PSA was used as an internal reference electrode. Next, signal antibodies of PSA-labeled CuS QDs as PEC signal quenchers were immobilized on the electrodes to form a sandwich-type immunocomplex. With the aid of a multiplexed disjunctor, the PEC responses of the dual electrodes were recorded, and the PSA was quantified via the ratio values of photocurrent intensities from WE1 and WE2. Combining the fine PEC performance of the CdS@g-C3N4 heterojunction with the superior quenching effect of CuS QDs in the spatial-resolved platform, the ratiometric system exhibits a linear range from 1.0 × 10-11 to 5.0 × 10-8 g mL-1 with a limit of detection of 4.0 pg mL-1. The results demonstrated herein may provide a new pattern for biomarker detection with high accuracy and good specificity as well as satisfactory applicability in real biosamples.