Sandwich photoelectrochemical biosensing of concanavalin A based on CdS/AuNPs/NiO Z-scheme heterojunction and lectin-sugar binding

A CdS/AuNPs/NiO Z-scheme heterojunction was prepared on a fluorine-doped tin oxide (FTO) electrode by hydrothermal synthesis of NiO on FTO, electrodeposition of AuNPs on NiO/FTO electrode and then cast-coating of CdS quantum dots. The CdS/AuNPs/NiO/FTO electrode gave a notably increased photocurrent versus NiO/FTO, CdS/FTO, AuNPs/NiO/FTO, CdS/AuNPs/FTO and CdS/NiO/FTO electrodes. The CdS/AuNPs/NiO/FTO electrode was further cast-coated with chitosan to immobilize d-mannose by Schiff base reaction, and concanavalin A (ConA) and then horseradish peroxidase (HRP) were captured on the electrode surface by lectin-sugar binding. 4-Chloro-1-naphthol (4-CN) was oxidized to form an insoluble precipitate catalyzed by HRP in the presence of H2O2, and the presence of precipitate on the photoelectrode inhibited the photocurrent in the presence of holes scavenger ascorbic acid. The relevant electrodes were characterized by electrochemistry, quartz crystal microbalance (QCM), UV-vis spectrophotometry, scanning electron microscopy/energy dispersive spectroscopy, and transmission electron microscopy. The QCM revealed that the collection efficiency (η) of the 4-CN-electrooxidation precipitate on the electrode can be as high as 91.8%. Under the optimal conditions, the decline of photocurrent responded linearly to the common logarithm of ConA concentration from 50 pM to 500 nM, with a limit of detection of 17 pM (S/N = 3). Satisfactory results were obtained in the detection of real soybean samples.