Skip to main content
SpringerLink
Log in

A versatile ratiometric nanosensing approach for sensitive and accurate detection of Hg2+ and biological thiols based on new fluorescent carbon quantum dots

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Herein, we first reported a facile synthesis method for fabrication of highly photoluminescent carbon quantum dots (CQDs) using sodium alginate as the carbon source and histidine as both the nitrogen source and functional monomer by one-pot hydrothermal synthesis. The as-prepared CQDs gave a high quantum yield of 32%. By employing the new CQDs and rhodamine B (RhB), we demonstrated a simple, facile, sensitive, and accurate ratiometric sensor for detection of Hg2+ and biological thiols. The photoluminescence of CQDs in the ratiometric sensor can be selectively and intensively suppressed by Hg2+ due to strong electrostatic interaction between the surface functional groups of the CQDs and Hg2+. When glutathione (GSH) was introduced into the “Turn Off” CQDs-RhB-Hg2+ sensing system, the fluorescence of the CQDs can be recovered rapidly due to the stronger affinity between thiol and Hg2+, while the fluorescence of the RhB remained constant in this sensing process. Based on the above principle, the ratiometric strategy for detecting Hg2+ and GSH can be achieved readily, and gives satisfactory limit of detections (LODs) of 30 and 20 nM for Hg2+ and GSH, respectively. The dual-emission fluorescent CQDs-RhB sensor does not need the complicated molecular design and the synthesis of dual-emission fluorophores. Meanwhile, the feasibility of the proposed method for analysis of water samples, food samples, and biological samples (plasma from mice oxidative stress study) was investigated. The developed ratiometric nanosensor is proven to be facile, with less sample consumption, rapid, lost cost, highly sensitive, and very selective for Hg2+ and biological thiol detection, which offers a new approach for environmental, food, and biological analysis.

Ratiometric nanosensing approach detection of Hg2+ and biological thiols

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
Fig. 6

Similar content being viewed by others

References

  1. Lim SY, Shen W, Gao Z. Carbon quantum dots and their applications. Chem Soc Rev. 2015;44:362–81.

    Article  CAS  Google Scholar 

  2. Salinas-Castillo A, Morales DP, Lapresta-Fernández A, et al. Evaluation of a reconfigurable portable instrument for copper determination based on luminescent carbon dots. Anal Bioanal Chem. 2016;408:3013–20.

    Article  CAS  Google Scholar 

  3. Fu Z, Li G, Hu Y. Chemiluminescence of nitrogen-rich quantum dots in diperiodatoargentate(III) solution and its application in ferulic acid analysis. Anal Bioanal Chem. 2016:1–8.

  4. Lisdat F, Schäfer D, Kapp A. Quantum dots on electrodes—new tools for bioelectroanalysis. Anal Bioanal Chem. 2013;405:3739–52.

    Article  CAS  Google Scholar 

  5. Gong P, Wang J, Hou K, et al. Small but strong: the influence of fluorine atoms on formation and performance of graphene quantum dots using a gradient F-sacrifice strategy. Carbon. 2017;112:63–71.

    Article  CAS  Google Scholar 

  6. Lin VS, Chen W, Xian M, Chang CJ. Chemical probes for molecular imaging and detection of hydrogen sulfide and reactive sulfur species in biological systems. Chem Soc Rev. 2015;44:4596–618.

    Article  CAS  Google Scholar 

  7. Mei J, Tong J, Wang J, et al. Discriminative fluorescence detection of cysteine, homocysteine and glutathione via reaction-dependent aggregation of fluorophore-analyte adducts. J Mater Chem. 2012;22(33):17063–70.

    Article  CAS  Google Scholar 

  8. Park KS, Kim MI, Woo MA, et al. A label-free method for detecting biological thiols based on blocking of Hg 2+-quenching of fluorescent gold nanoclusters. Biosens Bioelectron. 2013;45:65–9.

    Article  Google Scholar 

  9. Gu J, Hu D, Wang W, et al. Carbon dot cluster as an efficient “off–on” fluorescent probe to detect Au (III) and glutathione. Biosens Bioelectron. 2015;68:27–33.

    Article  CAS  Google Scholar 

  10. Zhang L, Cai Q-Y, Li J, et al. A label-free method for detecting biothiols based on poly(thymine)-templated copper nanoparticles. Biosens Bioelectron. 2015;69:77–82.

    Article  CAS  Google Scholar 

  11. Niu L-Y, Guan Y-S, Chen Y-Z, Wu L-Z, Tung C-H, Yang Q-Z. BODIPY-based ratiometric fluorescent sensor for highly selective detection of glutathione over cysteine and homocysteine. J Am Chem Soc. 2012;134:18928–31.

    Article  CAS  Google Scholar 

  12. Zhang X-L, Zheng C, Guo S-S, Li J, Yang H-H, Chen G. Turn-on fluorescence sensor for intracellular imaging of glutathione using g-C3N4 Nanosheet–MnO2 sandwich nanocomposite. Anal Chem. 2014;86:3426–34.

    Article  CAS  Google Scholar 

  13. Wang Y, Jiang K, Zhu J, Zhang L, Lin H. A FRET-based carbon dot–MnO2 nanosheet architecture for glutathione sensing in human whole blood samples. Chem Commun. 2015;51:12748–51.

    Article  CAS  Google Scholar 

  14. Lee MH, Kim JS, Sessler JL. Small molecule-based ratiometric fluorescence probes for cations, anions, and biomolecules. Chem Soc Rev. 2015;44:4185–91.

    Article  CAS  Google Scholar 

  15. Zhou X, Kwon Y, Kim G, Ryu J-H, Yoon J. A ratiometric fluorescent probe based on a coumarin–hemicyanine scaffold for sensitive and selective detection of endogenous peroxynitrite. Biosens Bioelectron. 2015;64:285–91.

    Article  CAS  Google Scholar 

  16. Hou J, Dong J, Zhu H, Teng X, Ai S, Mang M. A simple and sensitive fluorescent sensor for methyl parathion based on l-tyrosine methyl ester functionalized carbon dots. Biosens Bioelectron. 2015;68:20–6.

    Article  CAS  Google Scholar 

  17. Li G, Kong W, Zhao M, et al. 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. 2016;79:728–35.

    Article  CAS  Google Scholar 

  18. Zhu A, Qu Q, Shao X, Kong B, Tian Y. Carbon-dot-based dual-emission nanohybrid produces a ratiometric fluorescent sensor for in vivo imaging of cellular copper ions. Angew Chem. 2012;124:7297–301.

    Article  Google Scholar 

  19. Li G, Fu H, Chen X, et al. Facile and sensitive fluorescence sensing of alkaline phosphatase activity with photoluminescent carbon dots based on inner filter effect. Anal Chem. 2016;88(5):2720–6.

    Article  CAS  Google Scholar 

  20. Purbia R, Paria S. A simple turn on fluorescent sensor for the selective detection of thiamine using coconut water derived luminescent carbon dots. Biosens Bioelectron. 2016;79:467–75.

    Article  CAS  Google Scholar 

  21. Lan M, Zhang J, Chui Y-S, et al. Carbon nanoparticle-based ratiometric fluorescent sensor for detecting mercury ions in aqueous media and living cells. ACS Appl Mater Interfaces. 2014;6:21270–8.

    Article  CAS  Google Scholar 

  22. Lan M, Zhang J, Chui Y-S, et al. A recyclable carbon nanoparticle-based fluorescent probe for highly selective and sensitive detection of mercapto biomolecules. J Mater Chem B. 2015;3:127–34.

    Article  CAS  Google Scholar 

  23. Gupta A, Chaudhary A, Mehta P, et al. Nitrogen-doped, thiol-functionalized carbon dots for ultrasensitive Hg (II) detection. Chem Commun. 2015;51:10750–3.

    Article  CAS  Google Scholar 

  24. Xu H, Hepel M. “Molecular beacon”-based fluorescent assay for selective detection of glutathione and cysteine. Anal Chem. 2011;83(3):813–9.

    Article  CAS  Google Scholar 

  25. Jung HS, Chen X, Kim JS, et al. Recent progress in luminescent and colorimetric chemosensors for detection of thiols. Chem Soc Rev. 2013;42(14):6019–31.

    Article  CAS  Google Scholar 

  26. Zhang N, Qu F, Luo HQ, Li NB. Sensitive and selective detection of biothiols based on target-induced agglomeration of silvernanoclusters. Biosens Bioelectron. 2013;42:214–8.

    Article  CAS  Google Scholar 

  27. Cai Q-Y, Li J, Ge J, et al. A rapid fluorescence “switch-on” assay for glutathione detection by using carbon dots–MnO 2 nanocomposites. Biosens Bioelectron. 2015;72:31–6.

    Article  CAS  Google Scholar 

  28. Han B, Yuan J, Wang E. Sensitive and selective sensor for biothiols in the cell based on the recovered fluorescence of the CdTe quantum dots—Hg (II) system. Anal Chem. 2009;81:5569–73.

    Article  CAS  Google Scholar 

  29. Liu J, Bao C, Zhong X, Zhao C, Zhu L. Highly selective detection of glutathione using a quantum-dot-based OFF–ON fluorescent probe. Chem Commun. 2010;46:2971–3.

    Article  CAS  Google Scholar 

  30. Xu Y, Niu X, Zhang H, et al. 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. 2015;63:1747–55.

    Article  CAS  Google Scholar 

  31. Shi Y, Pan Y, Zhang H, et al. A dual-mode nanosensor based on carbon quantum dots and gold nanoparticles for discriminative detection of glutathione in human plasma [J]. Biosens Bioelectron. 2014;56:39–45.

    Article  CAS  Google Scholar 

  32. Vedi M, Rasool M, Sabina EP. Amelioration of bromobenzene hepatotoxicity by Withania somnifera pretreatment: role of mitochondrial oxidative stress. Toxicol Rep. 2014;1:629–38.

    Article  CAS  Google Scholar 

  33. Saha A, Jana NR. Detection of cellular glutathione and oxidized glutathione using magnetic–plasmonic nanocomposite-based “Turn-Off” surface enhanced raman scattering. Anal Chem. 2013;85:9221–8.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21677085, 31301595, 21475074, 81303179, 21305076, and 21475075), the Project funded by China Postdoctoral Science Foundation (No. 2016M590071), The Natural Science Foundation of Shandong Province (ZR2013BQ019 and ZR2016EMB04), Project of Shandong Province Higher Educational Science and Technology Program (J16LA03), the National Science and Technology Support Program of China (No. 2015BAD16B02), and National Undergraduate Training Program for Innovation and Entrepreneurship (No. 201510446060). We also thank Dr. Shuwei Sun for his good advice in the preparation of N-doped carbon quantum dots.

Author information

Author notes

    Authors and Affiliations

    1. Key Laboratory of Life-Organic Analysis of Shandong Province, Qufu Normal University, Qufu, Shandong, 273165, China

      Huili Fu, Zhongyin Ji, Xuejie Chen, Peiwei Gong, Guoliang Li, Guang Chen, Zhiwei Sun, Xianen Zhao, Feng Cheng & Jinmao You

    2. Institute of Agro-food Science and Technology, Shandong Academy of Agricultural Sciences, Jinan, Shandong, 250100, China

      Anwei Cheng

    3. Guangdong Provincial Key Laboratory of Aquatic Product Processing and Safety, College of Food Science and Technology, Guangdong Ocean University, Zhanjiang, Guangdong, 524000, China

      Shucheng Liu

    Authors
    1. Huili Fu
      View author publications

      You can also search for this author in PubMed Google Scholar

    2. Zhongyin Ji
      View author publications

      You can also search for this author in PubMed Google Scholar

    3. Xuejie Chen
      View author publications

      You can also search for this author in PubMed Google Scholar

    4. Anwei Cheng
      View author publications

      You can also search for this author in PubMed Google Scholar

    5. Shucheng Liu
      View author publications

      You can also search for this author in PubMed Google Scholar

    6. Peiwei Gong
      View author publications

      You can also search for this author in PubMed Google Scholar

    7. Guoliang Li
      View author publications

      You can also search for this author in PubMed Google Scholar

    8. Guang Chen
      View author publications

      You can also search for this author in PubMed Google Scholar

    9. Zhiwei Sun
      View author publications

      You can also search for this author in PubMed Google Scholar

    10. Xianen Zhao
      View author publications

      You can also search for this author in PubMed Google Scholar

    11. Feng Cheng
      View author publications

      You can also search for this author in PubMed Google Scholar

    12. Jinmao You
      View author publications

      You can also search for this author in PubMed Google Scholar

    Corresponding authors

    Correspondence to Guoliang Li or Jinmao You.

    Ethics declarations

    Conflict of interest

    The authors declare that they have no competing interests

    Animal treatment

    Kunming mice were obtained from animal house, China Biologic Products, Inc. This study was performed strictly according to the standards described in the “Guide for the Care and Use of Laboratory Animals” (National Research Council Commission on Life Sciences, 1996 edition). All animal treatment procedures were approved by the Animal Care Committee of Qufu Normal University, and all efforts were made to minimize suffering.

    Additional information

    Huili Fu and Zhongyin Ji contributed equally to this work.

    Electronic supplementary material

    Below is the link to the electronic supplementary material.

    ESM 1

    (PDF 268 kb)

    Rights and permissions

    Reprints and permissions

    About this article

    Check for updates. Verify currency and authenticity via CrossMark

    Cite this article

    Fu, H., Ji, Z., Chen, X. et al. 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 409, 2373–2382 (2017). https://doi.org/10.1007/s00216-017-0183-3

    Download citation

    • Received:

    • Revised:

    • Accepted:

    • Published:

    • Issue Date:

    • DOI: https://doi.org/10.1007/s00216-017-0183-3

    Keywords

    Search

    Navigation