Ultrasensitive sandwich-type photoelectrochemical immunosensor based on CdSe sensitized La-TiO2 matrix and signal amplification of polystyrene@Ab2 composites.

A novel and sensitive sandwich-type photoelectrochemical (PEC) sensor was fabricated using signal amplification strategy for the quantitative detection of the prostate specific antigen (PSA). CdSe nanoparticles (NPs) sensitized lanthanum-doped titanium dioxide (La-TiO2) composites were used to bind the primary antibodies (Ab1). The doping of lanthanum promoted the visible light absorption of TiO2 and remarkably enhanced the photocurrent. Moreover, 0.3%La-TiO2 displayed the highest photocurrent in the La-TiO2 composites, which was twice as much as that of undoped TiO2. Carboxyl modified CdSe NPs were assembled onto La-TiO2 composites via the dentate binding between -COOH and Ti atom in TiO2 NPs, which dramatically promoted the photocurrent intensity by approximately 2.1 times. Carboxyl functionalized polystyrene (PS) microspheres were coated with the secondary antibodies (Ab2). Owing to the better insulation property and steric hindrance of the prepared polystyrene@Ab2 (PS@Ab2) composites, the significant reduction of the photocurrent signal was achieved after the specific immune recognition. Under the optimum experimental conditions, the fabricated PEC sensor realized ultrasensitive detection of PSA in the range of 0.05-100pgmL(-1) with a detection limit of 17fgmL(-1). Moreover, this well-designed PEC immunoassay exhibited ideal reproducibility, stability, and selectivity, which is a promising platform for the detection of other important tumor targets.