A visual ratiometric fluorescence sensor for glutathione response based on MnO2 nanowires as an oxidant, quencher and recognition unit

Abstract

As the “mother of antioxidants”, glutathione (GSH) plays an important role in physiological functions. Rapid and accurate monitoring of GSH is of great significance for medicinal chemistry, food chemistry, and clinical medicine. We herein report a visual ratiometric fluorescence sensor based on MnO₂ nanowires (MnO₂ NWs) as an oxidant, quencher and recognition unit for the determination of GSH. The powerful ratiometric fluorescent probe was constructed by mixing thiamine (VB₁) and rhodamine B (RhB) with the help of MnO₂ NWs. MnO₂ NWs could not only effectively quench the fluorescence of RhB due to the inner filter effect (IFE), but also oxidized non-fluorescent VB₁ to blue fluorescent thiochrome (oxVB₁). Upon interaction with GSH, the quenched RhB fluorescence could be rapidly restored through decomposition of MnO₂ NWs into Mn²⁺, while the oxVB₁ fluorescence decreased, showing an apparent color change from blue to red. The concentration of GSH was proportional to the ratio of fluorescence intensities of RhB and oxVB₁, and the detection linear range was 1 to 10 000 μM with comparable selectivity. This ratio fluorescence sensor was successfully applied to GSH determination in whitening capsules and glutathione tablets with satisfactory results, and the sensor may be a potentially powerful tool for the detection of GSH.