Application of graphene-copper sulfide nanocomposite modified electrode for electrochemistry and electrocatalysis of hemoglobin.

In this paper a graphene (GR) and copper sulfide (CuS) nanocomposite was synthesized by hydrothermal method and used for the electrode modification with a N-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. Hemoglobin (Hb) was immobilized on the modified electrode to get a biocompatible sensing platform. UV-vis absorption spectroscopic results confirmed that Hb retained its native secondary structure in the composite. Direct electron transfer of Hb incorporated into the nanocomposite was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electrochemistry of Hb on the modified electrode. The results can be ascribed to the presence of GR-CuS nanocomposite on the electrode surface that facilitates the electron transfer rate between the electroactive center of Hb and the electrode. The Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 3.0 to 64.0 mmol L(-1) with the detection limit of 0.20 mmol L(-1) (3σ). The fabricated biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability.

Direct electrochemistry and electrocatalysis of hemoglobin in graphene oxide and ionic liquid composite film.

In this paper a novel sensing platform based on graphene oxide (GO), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate and Nafion for the immobilization of hemoglobin (Hb) was adopted with a carbon ionic liquid electrode (CILE) as the substrate electrode, which was denoted as Nafion/Hb-GO-IL/CILE. Spectroscopic results suggested that Hb molecules were not denatured in the composite. A pair of well-defined redox peaks appeared on the cyclic voltammogram, which was attributed to the realization of direct electron transfer of Hb on the electrode. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with the electrochemical parameters calculated. Based on the catalytic ability of the immobilized Hb, Nafion/Hb-GO-IL/CILE exhibited excellent electrocatalytic behavior towards the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.01 to 40.0mM with the detection limit as 3.12 µM (3σ), H2O2 in the concentration range from 0.08 to 635.0 µM with the detection limit as 0.0137 µM (3σ) and NaNO2 in the concentration range from 0.5 to 800.0 µM with the detection limit as 0.0104 µM (3σ). So the proposed bioelectrode could be served as a new third-generation electrochemical sensor without mediator.