Photocatalysis of TiO2 Sensitized with Graphitic Carbon Nitride and Electrodeposited Aryl Diazonium on Screen-Printed Electrodes to Detect Prostate Specific Antigen under Visible Light.

We report on a photoelectrochemical (PEC) device to detect prostatic-specific antigen (PSA) under visible LED light irradiation within the point-of-care (POC) paradigm. The device consists of a 3D printed miniaturized photoelectrochemical system and a disposable PEC immunosensor made with screen-printed carbon electrodes (SPCEs). The SPCEs were coated with nickel single atoms anchored on graphitic carbon nitride (Ni-gC3N4), titanium dioxide nanoparticles (TiO2), and aryl diazonium salt prepared from p-aminobenzoic acid. The electrodeposited aryl diazonium on Ni-gC3N4/TiO2 decreased the recombination of photogenerated charge carriers, leading to a 3.1-fold increase in the photocurrent compared to pure TiO2. This functionalization strategy provides carboxylic groups to anchor antibodies via the carbodiimide reaction, which may be extended to any other type of immunosensor. Under optimal conditions, the PEC immunosensor was able to detect PSA from 10-16 to 10-8 g mL-1 with a detection limit of 0.06 fg mL-1. The device robustness was confirmed with reproducibility and stability tests. PSA could also be detected in human serum samples, which demonstrates the potential of the PEC immunosensor for clinical diagnosis.