Electrochemical biosensor based on singlet oxygen generated by molecular photosensitizers

Here a sensing strategy with the integration of photosensitizer and electrochemical analysis was present. The photosensitizer, Zinc(II) tetraphenylporphyrin (ZnTCPP), was functionalized graphene oxide (GO) to form complex (ZnTCPP/GO) as the electrode material and generated singlet-oxygen (¹O₂) in the presence of air under light illumination. Due to the special electronic structure of ¹O₂, hydroquinone (HQ) could react with ¹O₂ to produce electrochemically-detectable products, benzoquinone (BQ). Meanwhile, the formed BQ could be reduced on the electrode, completing the redox cycling. The ZnTCPP/GO modified ITO electrode produces a stable and enhanced photocurrent signal under 420 nm irradiation in air-saturated buffer, compared with in N₂-saturated buffer. On the other hand, l-glutathione (GSH) as a signalling molecule plays important role in physiological process, which was employed as model to investigated the sensing performance. Coupling with HQ oxidized by ¹O₂, a GSH sensor was constructed on the basis the redox cycling of HQ. A sensitive reduction of photocurrent is observed with the addition of GSH, due to the GSH could be oxidized by the generated ¹O₂ to form GSSG. The biosensor displayed good performance in a broad concentration range of 0-150 μM, with a lower detection limit of 1.3 μM at an S/N ratio of 3, and could be used in practical application. This work affords a platform for constructing the biosensor with ¹O₂ instead of enzyme via on/off light switching.