Dual-Channel Photoelectrochemical Ratiometric Aptasensor with Up-converting Nanocrystals Using Spatial-Resolved Technique on Homemade 3D Printed Device

摘要： A near-infrared light (NIRL)-activated ratiometric photoelectrochemical (PEC) aptasensor was fabricated for detection of carcinoembryonic antigen (CEA) coupling with upconversion nanoparticles (UCNPs)-semiconductor nanocrystals-based spatial-resolved technique on a homemade 3D printing device in which a self-regulating integrated electrode was designed for dual signal readout. The as-prepared NaYF4:Yb, Er UCNPs@CdTe nanocrystals were initially assembled on two adjacent photoelectrodes, then CEA aptamer 1 (A1) and capture DNA (CA) were modified onto two working photoelectrodes (WP1 and WP2) through covalent binding, respectively, and then gold nanoparticle-labeled CEA aptamer 2 (Au NP-A2) were immobilized on the surface of functional WP2 for the formation of double-stranded DNA. Upon target CEA introduction, the various concentrations of CEA were captured on the WP1, whereas the binding of the CEA with Au NP-A2 could be released from the WP2 thanks to the highly affinity of CEA toward A2. The dual signal readout with the 'signal-off' of WP1 and 'signal-on' of WP2 were employed for the spatial-resolved PEC (SR-PEC) strategy to detect CEA as an analytical model. Combining NaYF4:Yb, Er UCNPs@CdTe nanocrystals with spatial-resolved model on 3D printing device, the PEC ratiometric aptasensor based on steric hindrance effect and exciton-plasmon interactions (EPI) exhibited a linear range from 10.0 pg mL-1 to 5.0 ng mL-1 with a limit of detection of 4.8 pg mL-1 under 980 nm illumination. The SR-PEC ratiometric strategy showed acceptable stability and reproducibility with a superior anti-interference ability. This approach can provide the guidance for the design of ratiometric, multiplexed and point-of-care biosensors.