SpringerLink
Log in

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

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price includes VAT (Germany)

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Liu J, Meng L, Fei Z, Dyson PJ, **g X, Liu X (2017) MnO2 nanosheets as an artificial enzyme to mimic oxidase for rapid and sensitive detection of glutathione. Biosens Bioelectron 90:69–74

    Article  CAS  Google Scholar 

  2. He L, Lu Y, Wang F, **g W, Chen Y, Liu Y (2018) Colorimetric sensing of silver ions based on glutathione-mediated MnO2 nanosheets. Sensors Actuators B Chem 254:468–474

    Article  CAS  Google Scholar 

  3. Currie LA (1968) Limits for qualitative detection and quantitative determination. Application to radiochemistry. Anal Chem 40:586–593

    Article  CAS  Google Scholar 

  4. Fang A, Chen H, Li H, Liu M, Zhang Y, Yao S (2017) Glutathione regulation-based dual-functional upconversion sensing-platform for acetylcholinesterase activity and cadmium ions. Biosens Bioelectron 87:545–551

    Article  CAS  Google Scholar 

  5. Shen R, Yang J, Luo H, Wang B, Jiang Y (2017) A sensitive fluorescent probe for cysteine and Cu2+ based on 1,8-naphthalimide derivatives and its application in living cells imaging. Tetrahedron 73:373–377

    Article  CAS  Google Scholar 

  6. Li Z, Wang Y, Ni Y (2015) A rapid and label-free dual detection of hg (II) and cysteine with the use of fluorescence switching of graphene quantum dots. Sensors Actuators B Chem 207:490–497

    Article  CAS  Google Scholar 

  7. Guo S, Liu G, Fan C, Pu S (2018) A new diarylethene-derived probe for colorimetric sensing of cu(II) and fluorometric sensing of cu(II) and Zn(II): Photochromism and high selectivity. Sensors Actuators B Chem 266:603–613

    Article  CAS  Google Scholar 

  8. Sheng J, Jiang X, Wang L, Yang M, Liu Y-N (2018) Biomimetic mineralization guided one-pot preparation of gold clusters anchored two-dimensional MnO2 Nanosheets for fluorometric/magnetic bimodal sensing. Anal Chem 90:2926–2932

    Article  CAS  Google Scholar 

  9. Zhou Y, Ma Z (2017) Fluorescent and colorimetric dual detection of mercury (II) by H2O2 oxidation of o-phenylenediamine using Pt nanoparticles as the catalyst. Sensors Actuators B Chem 249:53–58

    Article  CAS  Google Scholar 

  10. Zhu X, Li J, He H, Huang M, Zhang X, Wang S (2015) Application of nanomaterials in the bioanalytical detection of disease-related genes. Biosens Bioelectron 74:113–133

    Article  CAS  Google Scholar 

  11. **ong C, Zhang T, Kong W, Zhang Z, Qu H, Chen W, Wangn Y, Luo L, Zheng L (2018) ZIF-67 derived porous Co3O4 hollow nanopolyhedron functionalized solution-gated graphene transistors for simultaneous detection of glucose and uric acid in tears. Biosens Bioelectron 101:21–28

    Article  CAS  Google Scholar 

  12. Hu S, Zhu L, Lam CW (2019) Fluorometric determination of the activity of inorganic pyrophosphatase and its inhibitors by exploiting the peroxidase mimicking properties of a two-dimensional metal organic framework. Microchim Acta 186:190

    Article  Google Scholar 

  13. Zhang Q, Wang F, Zhang H, Zhang Y, Liu M, Liu Y (2018) Universal Ti3C2 MXenes based self-standard ratiometric fluorescence resonance energy transfer platform for highly sensitive detection of exosomes. Anal Chem 90:12737–12744

    Article  CAS  Google Scholar 

  14. Li L, Wang C, Liu K (2015) Hexagonal cobalt oxyhydroxide–carbon dots hybridized surface: high sensitive fluorescence turn-on probe for monitoring of ascorbic acid in rat brain following brain ischemia. Anal Chem 87:3404–3411

    Article  CAS  Google Scholar 

  15. Ganganboina AB, Doong RA (2018) The biomimic oxidase activity of layered V2O5 nanozyme for rapid and sensitive nanomolar detection of glutathione. Sensors Actuators B Chem 273:1179–1186

    Article  CAS  Google Scholar 

  16. Wei W, Cui X, Chen W, Ivey DG (2011) Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev 40:1697–1721

    Article  CAS  Google Scholar 

  17. Liu Z, Xu K, Sun H, Yin S (2015) One-step synthesis of single-layer MnO2 nanosheets with multi-role sodium dodecyl sulfate for high-performance pseudocapacitors. Small 11:2182–2191

    Article  CAS  Google Scholar 

  18. **ao T, Sun J, Zhao J, Wang S, Liu G, Yang X (2018) FRET effect between fluorescent polydopamine nanoparticles and MnO2 nanosheets and its application for sensitive sensing of alkaline phosphatase. ACS Appl Mater Interfaces 10:6560–6569

    Article  CAS  Google Scholar 

  19. Han L, Zhang H, Chen D, Li F (2018) Protein-directed metal oxide nanoflakes with tandem enzyme-like characteristics: colorimetric glucose sensing based on one-pot enzyme-free cascade catalysis. Adv Funct Mater 28:1800018

    Article  Google Scholar 

  20. Deng R, **e X, Vendrell M, Chang Y-T, Liu X (2011) Intracellular glutathione detection using MnO2-nanosheet-modified upconversion nanoparticles. J Am Chem Soc 133:20168–20171

    Article  CAS  Google Scholar 

  21. Wang X, Wang D, Guo Y, Yang C, Liu X, Iqbal A, Liu W, Qin W, Yan D, Guo H (2016) Fluorescent glutathione probe based on MnO2-phenol formaldehyde resin nanocomposite. Biosens Bioelectron 77:299–305

    Article  CAS  Google Scholar 

  22. Wang Q, Zhang Y, Wang X, Wu Y, Dong C, Shuang S (2019) Dual role of BSA for synthesis of MnO2 nanoparticles and their mediated fluorescent turn-on probe for glutathione determination and cancer cell recognition. Analyst. https://doi.org/10.1039/c8an02501k

  23. Qin J, Zhang L, Yang R (2019) Powder carbonization to synthesize novel carbon dots derived from uric acid for the detection of Ag(I) and glutathione. Spectrochim Acta A Mol Biomol Spectrosc 20:754–760

    Google Scholar 

  24. Xu J, Liu N, Hao C, Han Q, Duan Y, Wu J (2019) A novel fluorescence “on-off-on” peptide-based chemosensor for simultaneous detection of Cu2+, Ag+ and S2−. Sensors Actuators B Chem 280:129–137

    Article  CAS  Google Scholar 

  25. He L, Lu Y, Gao X (2018) Self-cascade system based on cupric oxide nanoparticles as dual-functional enzyme mimics for ultrasensitive detection of silver ions. ACS Sustain Chem Eng 6:12132–12139

    Article  CAS  Google Scholar 

  26. Ni P, Sun Y, Dai H, Hu J, Jiang S, Wang Y, Li Z (2015) Highly sensitive and selective colorimetric detection of glutathione based on Ag [I] ion-3,3,5,5-tetramethylbenzidine (TMB). Biosens Bioelectron 63:47–52

    Article  CAS  Google Scholar 

  27. Li F, Liu J, Hu Y, Deng N, He J (2018) An ultrasensitive label-free colorimetric assay for glutathione based on Ag+ regulated autocatalytic oxidation of o-phenylenediamine. Talanta 186:330–336

    Article  CAS  Google Scholar 

  28. Liu X, Wang Q, Zhao H, Zhang L, Su Y, Lv Y (2012) BSA-templated MnO2 nanoparticles as both peroxidase and oxidase mimics. Analyst 137:4552–4558

    Article  CAS  Google Scholar 

  29. Ge J, Cai R, Chen X, Wu Q, Zhang L, Jiang Y, Tan W (2019) Facile approach to prepare HSA-templated MnO2 nanosheets as oxidase mimic for colorimetric detection of glutathione. Talanta 195:40–45

    Article  CAS  Google Scholar 

  30. Rong S, Zhang P, Yang Y, Zhu L, Wang J, Liu F (2017) MnO2 framework for instantaneous mineralization of carcinogenic airborne formaldehyde at room temperature. ACS Catal 7:1057–1067

    Article  CAS  Google Scholar 

  31. Qu Z, Bu Y, Qin Y, Wang Y, Fu Q (2013) The improved reactivity of manganese catalysts by Ag in catalytic oxidation of toluene. Appl Catal B Environ 132:353–362

    Article  Google Scholar 

  32. Zeng R, Tang Y, Zhang L, Luo Z, Tang D (2018) Dual-readout aptasensing of antibiotic residues based on gold nanocluster-functionalized MnO2 nanosheets with target-induced etching reaction. J Mater Chem B 6:8071–8077

    Article  CAS  Google Scholar 

  33. Na W, Li N, Su X (2018) Enzymatic growth of single-layer MnO2 nanosheets in situ: application to detect alkaline phosphatase and ascorbic acid in the presence of sulfanilic acid functionalized graphene quantum dots. Sensors Actuators B Chem 274:172–179

    Article  CAS  Google Scholar 

  34. Zhang L, Zhang J, Chen H, Wang L (2018) Redox luminescence switch based on Mn2+-doped NaYF4:Yb,Er upconversion nanorods. Luminescence 33:138–144

    Article  CAS  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

  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

Authors
  1. Zhangyan Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tengteng Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peipei Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Meiling Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Si Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Haitao Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Youyu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Shouzhuo Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Meiling Liu.

Ethics declarations

The author(s) declare that they have no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOC 277 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

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

Keywords

Search

Navigation