Construction of a Dual-Mode Biosensor with Ferrocene as Both a Signal Enhancer and a Signal Tracer for Electrochemiluminescent and Electrochemical Enantioselective Recognition

We demonstrate for the first time the construction of a dual-mode biosensor for electrochemiluminescent (ECL) and electrochemical chiral recognition of l- and d-isomers of amino acids, with ferrocene (Fc) as both a signal enhancer and a signal tracer. With the dissolved oxygen as a coreactant, ZnIn2S4 acts as the ECL emitter to generate a weak cathodic ECL signal. Fc can enter into the β-cyclodextrin (β-CD) cavity on ZnIn2S4-modified electrode as a result of host–guest interaction. Since Fc can promote H2O and O2 to produce abundant reactive oxygen species (ROS) (e.g., O2·– and ·OH), the ECL signal of ZnIn2S4 can be further amplified with Fc as a coreaction accelerator. Meanwhile, Fc molecules on the β-CD/ZnIn2S4-modified electrode can be electrochemically oxidized to Fc+ to produce a remarkable oxidation peak current. When l-histidine (l-His) is present, the matching of the l-His configuration with the β-CD cavity leads to the entrance of more l-His into the cavity of β-CD than d-histidine (d-His), and the subsequent competence of l-His with Fc on the Fc/β-CD/ZnIn2S4-modified electrode induces the decrease in both Fc peak current and ZnIn2S4-induced ECL intensity. This dual-mode biosensor can efficiently discriminate l-His from d-His, and it can sensitively monitor l-His with a detection limit of 7.60 pM for ECL mode and 3.70 pM for electrochemical mode. Moreover, this dual-mode biosensor can selectively discriminate l-His from other l- and d-isomers (e.g., threonine, phenylalanine, and glutamic acid), with potential applications in the chiral recognition of nonelectroactive chiral compounds, bioanalysis, and disease diagnosis.