Microstructural and electrochemical impedance characterization of bio-functionalized ultrafine ZnS nanocrystals–reduced graphene oxide hybrid for immunosensor applications

Abstract

We report a mercaptopropionic acid capped ZnS nanocrystals decorated reduced graphene oxide (RGO) hybrid film on a silane modified indium-tin-oxide glass plate, as a bioelectrode for the quantitative detection of human cardiac myoglobin (Ag-cMb). The ZnS nanocrystals were anchored over electrochemically reduced GO sheets through a cross linker, 1-pyrenemethylamine hydrochloride, by carbodiimide reaction and have been characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The transmission electron microscopic characterization of the ZnS–RGO hybrid shows the uniform distribution of ultra-fine nanoparticles of ZnS in nano-sheets of GO throughout the material. The protein antibody, Ab-cMb, was covalently linked to ZnS–RGO nanocomposite hybrid for the fabrication of the bioelectrode. A detailed electrochemical immunosensing study has been carried out on the bioelectrode towards the detection of target Ag-cMb. The optimal fitted equivalent circuit model that matches the impedance response has been studied to delineate the biocompatibility, sensitivity and selectivity of the bioelectrode. The bioelectrode exhibited a linear electrochemical impedance response to Ag-cMb in a range of 10 ng to 1 μg mL⁻¹ in PBS (pH 7.4) with a sensitivity of 177.56 Ω cm² per decade. The combined synergistic effects of the high surface-to-volume ratio of ZnS(MPA) nanocrystals and conducting RGO has provided a dominant charge transfer characteristic (R_et) at the lower frequency region of <10 Hz showing a good biocompatibility and enhanced impedance sensitivity towards target Ag-cMb. The impedance response sensitivity of the ZnS–RGO hybrid bioelectrode towards Ag-cMb has been found to be about 2.5 fold higher than that of a bare RGO modified bioelectrode.