Dual-mode biosensor using Tb-Cu MOF@Au nanoenzyme to effectively quench the photocurrent of BiO/BiS/AgBiS heterojunction and emit fluorescence for neuron-specific enolases detection.

A novel dual-mode biosensor was constructed for the ultrasensitive detection of neuron-specific enolase (NSE), utilizing Tb-Cu MOF@Au nanozyme as the signal label to effectively quench the photoelectrochemical (PEC) signals of BiO/BiS/AgBiS composites and initiate fluorescent (FL) signals. First, BiO/BiS/AgBiS heterojunction with excellent photoelectric activity was selected as the substrate material to provide a stable photocurrent. The well-matched energy levels significantly enhanced the separation and transfer of photogenerated carriers. Second, a strategy of consuming ascorbic acid (AA) by Tb-Cu MOF@Au nanozyme was introduced to improve the sensitivity of the PEC/FL biosensor. Tb-Cu MOF@Au not only could catalyze the oxidation of AA, but the steric effect further reduced the contact of AA with the substrate. More importantly, in the presence of HO, a significant fluorescence was produced from Tb sensitized by the oxidation products of AA. Based on the above strategies, a highly stable and sensitive dual-mode biosensor was proposed for accurate NSE determination. Third, the developed dual-mode biosensor demonstrated excellent performance in detecting NSE. In this study, the PEC method demonstrated a wide detection range from 0.00005 to 200 ng/mL with a low detection limit of 20 fg/mL. The FL method exhibited a linear range from 0.001 to 200 ng/mL with a detection limit of 0.65 pg/mL. The designed biosensor showed potential practical implications in the accurate detection of disease markers.