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 Ag(2)S, 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(−1) with favorable repeatability, specificity, and acceptable method accuracy. The detection limit was as low as 0.06 pg mL(−1). In addition, this strategy provided new thought for the test of other small-molecule analytes and immunosensor applied in the complex biological system. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00216-022-03893-z.