Skip to main content
SpringerLink
Log in

Fluorometric determination and imaging of glutathione based on a thiol-triggered inner filter effect on the fluorescence of carbon dots

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

Abstract

The authors describe a sensitive method for determination of glutathione (GSH) that is based on a thiol-triggered inner filter effect on the fluorescence of N-doped carbon dots (N-doped CDs). N-doped CDs with a quantum yield as high as 31% were prepared by a one-pot procedure, and 5,5′-dithiobis-(2-nitrobenzoic acid) was employed as a reagent for GSH recognition. The reaction product (5-thio-2-nitrobenzoic acid; TNB) acts as an absorber of the 410-nm light used to photo-excite the N-doped CDs. Hence, the fluorescence of N-doped CDs (peaking at 510 nm) is reduced with increasing concentrations of GSH. As little as 30 nM of GSH can be detected by this method. The approach was successfully applied to (a) food analysis, (b) an investigation of an oxidative stress model, and (c) to live cells imaging. The method does not require the surface of N-doped CDs to be chemically modified, and a linkage between receptor and fluorophore is not needed. In our perception, the method may become a viable tool for the detection and imaging of thiols.

Fluorescence sensing strategy for glutathione detection based on a thiol-triggered inner filter effect via new N-doped carbon dots and application to food analysis, oxidative stress study and cell imaging.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Sies H (2013) Oxidative stress. Elsevier

  2. Xu Y, Niu X, Zhang H, Xu L, Zhao S, Chen H, Chen X (2015) Switch-on fluorescence sensing of glutathione in food samples based on a graphitic carbon nitride quantum dot (g-CNQD)–Hg2+ Chemosensor. J Agric Food Chem 63(6):1747–1755

    Article  CAS  Google Scholar 

  3. Guo Z, Park S, Yoon J, Shin I (2014) Recent progress in the development of near-infrared fluorescent probes for bioimaging applications. Chem Soc Rev 43(1):16–29

    Article  Google Scholar 

  4. Tang Y, Lee D, Wang J, Li G, Yu J, Lin W, Yoon J (2015) Development of fluorescent probes based on protection–deprotection of the key functional groups for biological imaging. Chem Soc Rev 44(15):5003–5015

    Article  CAS  Google Scholar 

  5. Jung H, Chen X, Kim J, Yoonet J (2013) Recent progress in luminescent and colorimetric chemosensors for detection of thiols. Chem Soc Rev 42(14):6019–6031

    Article  CAS  Google Scholar 

  6. Biju V (2014) Chemical modifications and bioconjugate reactions of nanomaterials for sensing, imaging, drug delivery and therapy. Chem Soc Rev 43(3):744–764

    Article  CAS  Google Scholar 

  7. Dong JX, Song XF, Shi Y, Gao ZF, Li BL, Li NB, Luo HQ (2016) A potential fluorescent probe: Maillard reaction product from glutathione and ascorbic acid for rapid and label-free dual detection of Hg2+ and biothiols. Biosens Bioelectron 81:473–479

    Article  CAS  Google Scholar 

  8. Ju J, Zhang R, He S, Chen W (2014) Nitrogen-doped graphene quantum dots-based fluorescent probe for the sensitive turn-on detection of glutathione and its cellular imaging. RSC Adv 4(94):52583–52589

    Article  CAS  Google Scholar 

  9. Tang W, Wang Y, Wang P, Di J, Yang J, Wu Y (2016) Synthesis of strongly fluorescent carbon quantum dots modified with polyamidoamine and a triethoxysilane as quenchable fluorescent probes for mercury(II). Microchim Acta 183(9):2571–2578

    Article  CAS  Google Scholar 

  10. Wang B, Chen Y, Wu Y, Weng B, Liu Y, Li C (2016) Synthesis of nitrogen- and iron-containing carbon dots, and their application to colorimetric and fluorometric determination of dopamine. Microchim Acta 183(9):2491–2500

    Article  CAS  Google Scholar 

  11. Li G, Kong W, Zhao M, Lu S, Gong P, Chen G, Xia L, Wang H, You J, Wu Y (2016) A fluorescence resonance energy transfer (FRET) based “turn-on” nanofluorescence sensor using a nitrogen-doped carbon dot-hexagonal cobalt oxyhydroxide nanosheet architecture and application to α-glucosidase inhibitor screening. Biosens Bioelectron 79:728–735

    Article  CAS  Google Scholar 

  12. Liu B, Han S (2016) Determination of trace hydrogen sulfide by using the permanganate induced chemiluminescence of carbon dots. Microchim Acta 183(11):3087–3092

    Article  CAS  Google Scholar 

  13. Cayuela A, Soriano ML, Carrillo-Carrion C, Valcarcel M (2016) Semiconductor and carbon-based fluorescent nanodots: the need for consistency. Chem Commun 52(7):1311–1326

    Article  CAS  Google Scholar 

  14. Lim SY, Shen W, Gao Z (2015) Carbon quantum dots and their applications. Chem Soc Rev 44(1):362–381

    Article  CAS  Google Scholar 

  15. Jiang X, Geng F, Wang Y, Liu J, Qu P, Xu M (2016) Fluorescence turn-on and colorimetric dual readout assay of glutathione over cysteine based on the fluorescence inner-filter effect of oxidized TMB on TMPyP. Biosens Bioelectron 81:268–273

    Article  CAS  Google Scholar 

  16. Xia N, Zhou B, Huang N, Jiang M, Zhang J, Liu L (2016) Visual and fluorescent assays for selective detection of beta-amyloid oligomers based on the inner filter effect of gold nanoparticles on the fluorescence of CdTe quantum dots. Biosens Bioelectron 85:625–632

    Article  CAS  Google Scholar 

  17. Chang H-C, Ho J-a A (2015) Gold Nanocluster-assisted fluorescent detection for hydrogen peroxide and cholesterol based on the inner filter effect of gold nanoparticles. Anal Chem 87(20):10362–10367

    Article  CAS  Google Scholar 

  18. Kim H, Lee B-I, Byeon S-H (2015) The inner filter effect of Cr (VI) on Tb-doped layered rare earth hydroxychlorides: new fluorescent adsorbents for the simple detection of Cr (VI). Chem Commun 51(4):725–728

    Article  Google Scholar 

  19. Li G, Fu H, Chen X, Gong P, Chen G, Xia L, Wang H, You J, Wu Y (2016) Facile and sensitive fluorescence sensing of alkaline phosphatase activity with Photoluminescent carbon dots based on inner filter effect. Anal Chem 88(5):2720–2726

    Article  CAS  Google Scholar 

  20. Yan X, Li H, Han X, Su X (2015) A ratiometric fluorescent quantum dots based biosensor for organophosphorus pesticides detection by inner-filter effect. Biosens Bioelectron 74:277–283

    Article  CAS  Google Scholar 

  21. Zhu S, Meng Q, Wang L, Zhang J, Song Y, Jin H, Zhang K, Sun H, Wang H, Yang B (2013) Highly photoluminescent carbon dots for multicolor patterning, sensors, and bioimaging. Angew Chem 125(14):4045–4049

    Article  Google Scholar 

  22. Wang N, Wang Y, Guo T, Yang T, Chen M, Wang J (2016) Green preparation of carbon dots with papaya as carbon source for effective fluorescent sensing of iron (III) and Escherichia coli. Biosens Bioelectron 85:68–75

    Article  CAS  Google Scholar 

  23. Li Z, Ni Y, Kokot S (2015) A new fluorescent nitrogen-doped carbon dot system modified by the fluorophore-labeled ssDNA for the analysis of 6-mercaptopurine and hg (II). Biosens Bioelectron 74:91–97

    Article  CAS  Google Scholar 

  24. Lan M, Zhang J, Chui Y-S, Wang H, Yang Q, Zhu X, Wei H, Liu W, Ge J, Wang P (2015) A recyclable carbon nanoparticle-based fluorescent probe for highly selective and sensitive detection of mercapto biomolecules. J Mater Chem B 3(1):127–134

    Article  CAS  Google Scholar 

  25. Riddles PW, Blakeley RL, Zerner B (1979) Ellman's reagent: 5, 5′-dithiobis (2-nitrobenzoic acid)-a reexamination. Anal Biochem 94(1):75–81

    Article  CAS  Google Scholar 

  26. Rahman I, Kode A, Biswas SK (2006) Assay for quantitative determination of glutathione and glutathione disulfide levels using enzymatic recycling method. Nat Protoc 1(6):3159–3165

    Article  CAS  Google Scholar 

  27. Guo Y, Yang L, Li W, Wang X, Shang Y, Li B (2016) Carbon dots doped with nitrogen and sulfur and loaded with copper (II) as a "turn-on" fluorescent probe for cystein, glutathione and homocysteine. Microchim Acta 183(4):1409–1416

    Article  CAS  Google Scholar 

  28. Zhang X-L, Zheng C, Guo S-S, Li J, Yang H-H, Chen G (2014) Turn-on fluorescence sensor for intracellular imaging of glutathione using g-C3N4 Nanosheet–MnO2 sandwich Nanocomposite. Anal Chem 86:3426–3434

    Article  CAS  Google Scholar 

  29. Han B, Yuan J, Wang E (2009) Sensitive and selective sensor for biothiols in the cell based on the recovered fluorescence of the CdTe quantum dots− hg (II) system. Anal Chem 81:5569–5573

    Article  CAS  Google Scholar 

  30. Cai QY, Li J, Ge J, Zhang L, Hua Y, Li Z, Qu L (2015) A rapid fluorescence “switch-on” assay for glutathione detection by using carbon dots–MnO2 nanocomposites. Biosens Bioelectron 72:31–36

    Article  CAS  Google Scholar 

  31. Zhang N, Qu F, Luo HQ, Li N (2013) Sensitive and selective detection of biothiols based on target-induced agglomeration of silver nanoclusters. Biosens Bioelectron 42:214–218

    Article  CAS  Google Scholar 

  32. Rahman M, Hussain M, Asiri A (2016) A glutathione biosensor based on a glassy carbon electrode modified with CdO nanoparticle-decorated carbon nanotubes in a nafion matrix. Microchim Acta 183(12):3255–3263

    Article  CAS  Google Scholar 

  33. Liu J, Bao C, Zhong X, Zhao C, Zhu L (2010) Highly selective detection of glutathione using a quantum-dot-based OFF–ON fluorescent probe. Chem Commun 46:2971–2973

    Article  CAS  Google Scholar 

  34. Fu H, Ji Z, Chen X, Cheng A, Liu S, Gong P, Li G, Chen G, Sun Z, Zhao X, Cheng F, You J (2017) A versatile ratiometric nanosensing approach for sensitive and accurate detection of Hg2+ and biological thiols based on new fluorescent carbon quantum dots. Anal Bioanal Chem. doi:10.1007/s00216-017-0183-3

    Google Scholar 

  35. Saha A, Jana NR (2013) Detection of cellular glutathione and oxidized glutathione using magnetic–Plasmonic Nanocomposite-based “turn-off” surface enhanced Raman scattering. Anal Chem 85(19):9221–9228

    Article  CAS  Google Scholar 

  36. Vedi M, Rasool M, Sabina EP (2014) Amelioration of bromobenzene hepatotoxicity by Withania somnifera pretreatment: role of mitochondrial oxidative stress. Toxicol Rep 1:629–638

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by The National Natural Science Foundation of China (No. 21677085, 21537001 and 81472986) and the Project funded by China Postdoctoral Science Foundation (No 2016 M590071).

Author information

Authors and Affiliations

  1. School of Life Sciences, Xiamen University, Xiamen, 361005, China

    Di Wu

  2. School of Food and Biological Engineering, Shaanxi University of Science & Technology, Xian, 710021, China

    Guoliang Li & Xuefeng Chen

  3. Key Laboratories of Chemical Safety and Health, China National Center for Food Safety Risk Assessment, Beijing, 100050, People’s Republic of China

    Guoliang Li, Nannan Qiu, Xuexiang Shi & Yongning Wu

  4. Key Laboratory of Life-Organic Analysis of Shandong Province, Qufu Normal University, Qufu, 273165, People’s Republic of China

    Guoliang Li, Guang Chen, Zhiwei Sun & Jinmao You

Authors
  1. Di Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Guoliang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xuefeng Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nannan Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xuexiang Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhiwei Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jinmao You
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yongning Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Guoliang Li or Yongning Wu.

Ethics declarations

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

Electronic supplementary material

ESM 1

(DOCX 485 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, D., Li, G., Chen, X. et al. Fluorometric determination and imaging of glutathione based on a thiol-triggered inner filter effect on the fluorescence of carbon dots. Microchim Acta 184, 1923–1931 (2017). https://doi.org/10.1007/s00604-017-2187-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-017-2187-2

Keywords

Search

Navigation