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A dual (colorimetric and fluorometric) detection scheme for glutathione and silver (I) based on the oxidase mimicking activity of MnO2 nanosheets

Microchimica Acta volume 186, Article number: 498 (2019) Cite this article

Abstract

A fluorimetric and colorimetric method is described for the determination of glutathione (GSH) and silver (I). It is based on the use of MnO2 nanosheets that were prepared by solution mixing and exfoliation. They display oxidase-mimicking activity and can catalyze the oxidation of o-phenylenediamine (OPD) to form yellow 2,3-diaminophenazine (DAP) with an absorption maximum at 410 nm. DAP also has a yellow fluorescence (with a peak at 560 nm). The MnO2 nanosheets can be rapidly reduced to Mn2+ by GSH. This reduces the efficiency of the oxidase mimic MnO2 and causes a decrease in fluorescence and absorbance intensity. However, on addition of Ag+, a complex is formed with GSH. It prevents the destruction of MnO2 nanosheets so that the enzyme mimicking activity is retained. A dual-method for the determination of GSH and Ag(I) was developed. It has excellent sensitivity for GSH with lower detection limits of 62 nM (fluorimetric) and 0.94 μM (colorimetric). The respective data for Ag(I) are 70 nM and 1.15 μM. The assay was successfully applied to the determination of GSH and Ag(I) in spiked serum samples.

Schematic presentation of a method for colorimetric and fluorometric determination of glutathione (GSH) and silver(I). MnO2 nanosheets are reduced to Mn(II) by GSH. This reduces the enzyme-mimicking activity of MnO2 nanosheets and causes a decrease in fluorescence and absorbance. On addition of Ag(I), the enzyme-like activity is increasingly retained. A decrease in fluorescence and absorbance is not observed any longer.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21645008, 21305042), Scientific Research Fund of Hunan Provincial Education Department (18A010, 17C0947), Science and Technology Department (14JJ4030), the construct program of the key discipline in Hunan province and the Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province.

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  1. Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education, China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, People’s Republic of China

    Zhangyan Ma, Tengteng Wu, Peipei Li, Meiling Liu, Si Huang, Haitao Li, Youyu Zhang & Shouzhuo Yao

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  1. Zhangyan Ma
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Correspondence to Meiling Liu.

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Ma, Z., Wu, T., Li, P. et al. A dual (colorimetric and fluorometric) detection scheme for glutathione and silver (I) based on the oxidase mimicking activity of MnO2 nanosheets. Microchim Acta 186, 498 (2019). https://doi.org/10.1007/s00604-019-3613-4

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  • DOI: https://doi.org/10.1007/s00604-019-3613-4

Keywords

  • MnO2 nanosheets
  • Dual-readout
  • Dual-component
  • Colorimetric and fluorometric method
  • GSH and Ag+