Using silver nanocluster/graphene nanocomposite to enhance photoelectrochemical activity of CdS:Mn/TiO2 for highly sensitive signal-on immunoassay

A highly sensitive signal-on photoelectrochemical (PEC) immunosensor was fabricated here using CdS:Mn/TiO2 as photoelectrochemical sensing platform, and silver nanoclusters and graphene naocomposites (AgNCs-GR) as signal amplification tags. The immunosensor was constructed based on the specific sandwich immunoreaction, and the photo-to-current conversion efficiency of the isolated protein modified CdS:Mn/TiO2 matrix was improved based on the synergistic effect of AgNCs-GR. Under irradiation, the photogenerated electrons from the AgNCs at a higher conduction band edge level could be transport to the CdS:Mn/TiO2 matrix with the assistance of highly conductive graphene nanosheets, as well as recycle the trapped excitons in the defects-rich CdS:Mn/TiO2 interface. The electron transport and exciton recycle reduced the possibility of electron-hole recombination and greatly improved the photo-to-current conversion efficiency of the sensing matrix. Based on the signal enhancement, a signal-on PEC immunosensors was fabricated for the detection of carcinoembryonic antigen (CEA), a model analyte related to many malignant diseases. Under optimal conditions, the as-prepared immunosensor showed excellent analytical performance, with a wide linear range from 1.0 pg/mL to 100 ng/mL and a low limit of detection of 1.0 pg/mL. The signal-on mode provided 2.48 times higher sensitivity compared with signal-off mode. This strategy demonstrated good accuracy and high selectivity for practical sample analysis, thus may have great application prospective in the prediction and early diagnosis of diseases.