Gold nanoparticles-immobilized, hierarchically ordered, porous TiO2 nanotubes for biosensing of glutathione

Glutathione (GSH) is vital for several functions of our human body such as neutralization of free radicals and reactive oxygen compounds, maintaining the active forms of vitamin C and E, regulation of nitric oxide cycle, iron metabolism, etc. It is also an endogenous antioxidant in most of the biological reactions. Given the importance of GSH, a simple strategy is proposed in this work to develop a biosensor for quantitative detection of GSH. This particular biosensor comprises of gold nanoparticles (Au NPs)-immobilized, hierarchically ordered titanium dioxide (TiO2) porous nanotubes. Hexagonally arranged, honeycomb-like nanoporous tubular TiO2 electrodes are prepared by using a simple electrochemical anodization process by applying a constant potential of 30 V for 24 hours using ethylene glycol consisting of ammonium fluoride as an electrolytic medium. Structural morphology and crystalline nature of such TiO2 nanotubes are analyzed using field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). Interestingly, nanocomposites of TiO2 with Au NPs is prepared in an effort to alter the intrinsic properties of TiO2, especially tuning of its band gap. Au NPs are prepared by a well-known Brust and Schiffrin method and are immobilized onto TiO2 electrodes which act as a perfect electrochemical sensing platform for GSH detection. Structural characterization and analysis of these modified electrodes are performed using FESEM, XRD, and UV-visible spectroscopic studies. GSH binding events on Au NPs-immobilized porous TiO2 electrodes are monitored by electrochemical techniques, namely, cyclic voltammetry (CV) and chronoamperometry (CA). Several parameters such as sensitivity, selectivity, stability, limit of detection, etc are investigated. In addition, Au NPs dispersed in aqueous medium are also explored for naked-eye detection of GSH using UV-visible spectroscopy in order to compare the performance of the proposed sensor. Our studies clearly indicate that these materials could potentially be used for GSH sensing applications.