Signal-on photoelectrochemical immunoassay for salivary cortisol based on silver nanoclusters-triggered ion-exchange reaction with CdS quantum dots.

Nowadays, the epidemic, employment, and academic pressures are seriously affecting our physical and mental health. Herein, we designed a magneto-controlled photoelectrochemical immunosensor for noninvasive monitoring of salivary cortisol regarded as a pressure biomarker. A competitive immunoassay model was established by coupling bovine serum albumin-cortisol modified magnetic beads (MB-BSA-cortisol) with silver nanoclusters (Ag NCs)-labelled anti-cortisol antibody, and quantity analysis was operated by photoelectrochemical measurement of the CdS/Au electrode as an ion-exchange platform. Accompanying the formation of immune complexes, the carried Ag NCs were readily dissolved with nitric acid to produce abundant silver ions, which transferred to the electrode for ion-exchange reaction with CdS quantum dots to produce AgS, a new electron-hole capture site, leading to a decrease in the photocurrent intensity. The photocurrent signal gradually recovered with the increase of concentration of target cortisol, acquiring the signal-on mode competitive immunosensing system, which is propitious to the detection of small molecules. Within optimal conditions, this sensor had a satisfactory linear relationship in the range of 0.0001-100 ng mL with favorable repeatability, specificity, and acceptable method accuracy. The detection limit was as low as 0.06 pg mL. In addition, this strategy provided new thought for the test of other small-molecule analytes and immunosensor applied in the complex biological system.