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Abstract: A homogeneous chitosan–ferrocene/graphene oxide/glucose oxidase (CS–Fc/GO/GOx) nanocomposite film was successfully constructed as a novel platform for the fabrication of glucose biosensor. The morphologies and electrochemistry of the nanocomposite film were investigated by using scanning electron microscopy and electrochemical techniques including electrochemical impedance spectroscopy and cyclic voltammetry, respectively. Results demonstrated that the uniformly dispersed GO within the CS matrix could significantly improve the stability of GO and make it exhibit a positive charge, which was more favorable for the further immobilization of biomolecules, such as GOx, with higher loading. Further attaching redox mediator ferrocene group (Fc) to CS could not only effectively prevent the leakage of Fc from the matrix and retain its electrochemical activity, but also improve the electrical conductivity of CS and promote the electron-transfer between GOx and electrode. Biosensors based on this CS–Fc/GO/GOx film had advantages of fast response, excellent reproducibility, high stability, and showed a linear response to glucose in the concentration range from 0.02 to 6.78mM with a detection limit of 7.6μM at a signal-to-noise ratio of 3 and exhibited a higher sensitivity of 10μAmM−1 cm−2. The proposed strategy based on CS–Fc/GO nanocomposite for the immobilization of enzymes can be of practical relevance for the facile design of biosensors, as well as for the construction of new multifunctional bioelectrochemical systems. [Copyright &y& Elsevier]

Abstract: A novel “smart” electrochemical affinity nanobiosensor with “on-off” switchable property was designed for the ultrasensitive determination of glucose. The sensing approach was based on the glucose-ConA-dextran competitive system induced charge evolution in the use of graphene oxide (GO) as transducer element, resulting in the enhancement of interfacial electron transfer kinetics between the redox probe and the electrode. As concanavalin A (ConA) constituent was pH-sensitive, when the ConA-DexP/GO film electrode switched in probe Fe(CN)6 3−/4− solution between pH 4.0 and 8.0, the film was cycled between the “on” and “off” states by the electrostatic attraction and repulsion of Fe(CN)6 3−/4− to and from the electrode surface. Upon introduction of glucose into the ConA-DexP/GO complex at the “off” state, glucose competed with DexP for ConA and displaced ConA from the GO platform, resulting in gradual decrease of the surface negative charge as well as the resistance of probe for electron communication on the sensor surface, and making the switching from “off” state to “on” state simultaneously. This ultrasensitive glucose nanobiosensor had a broad linearity between the decrease in electron transfer resistance (ΔR) and the glucose concentration over a range from 5.0μM to 9.0mM with a detection limit as low as 0.34μM. The proposed method showed potential application for fabricating novel biosensors and bioelectronic devices. [Copyright &y& Elsevier]