Skip to main content
SpringerLink
Log in

Carbon dots doped with nitrogen and sulfur and loaded with copper(II) as a “turn-on” fluorescent probe for cystein, glutathione and homocysteine

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

Abstract

We report on the synthesis of fluorescent carbon dots doped with nitrogen and sulfur (N,S-CDs) via a hydrothermal process in pure water and starting from a mixture of alfalfa and garlic. Compared to N-doped CDs, the N,S-CDs exhibit a high fluorescence quantum yield (10 %) and a more longwave emission maximum (at 481 nm). The results also pave the way to tune the luminescence of CDs. The fluorescence of the N,S-CDs is quenched by Cu(II) ions but is recovered by addition of any of the biothiols cystein, glutathione or homocysteine. This turn-on effect was exploited to design a method for the quantification of these thiols in concentrations as low as 86 nM. The method was successfully applied to the determination of Cys in (spiked) human serum samples.

Carbon dots doped with nitrogen and sulfur and loaded with copper(II) as a “turn-on” fluorescent probe for cystein, glutathione and homocysteine. Nitrogen and sulfur co-doped carbon dots with blue-green fluorescence are synthesized by one-step hydrothermal treatment of hybrid plant (alfalfa and garlic), and demonstrated as environmentally-friendly fluorescence probes for the sensing of biothiols with high sensitivity and selectivity.

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

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

Similar content being viewed by others

References

  1. Baker SN, Baker GA (2010) Luminescent carbon nanodots: emergent nanolights. Angew Chem Int Ed 49:6726–6744

    Article  CAS  Google Scholar 

  2. Wang Y, Hu A (2014) Carbon quantum dots: synthesis, properties and applications. J Mater Chem C 2:6921–6939

    Article  CAS  Google Scholar 

  3. Chen L, Han H (2014) Recent advances in the use of near-infrared quantum dots as optical probes for bioanalytical, imaging and solar cell application. Microchim Acta 181:1485–1495

    Article  CAS  Google Scholar 

  4. Cao L, Meziani MJ, Sahu S, Sun YP (2013) Photoluminescence properties of graphene versus other carbon nanomaterials. Acc Chem Res 46:171–180

    Article  CAS  Google Scholar 

  5. Li LL, Ji J, Fei R, Wang CZ, Lu Q, Zhang JR, Jiang LP, Zhu JJ (2012) A facile microwave avenue to electrochemiluminescent two-color graphene quantum dots. Adv Funct Mate 22:2971–2979

    Article  CAS  Google Scholar 

  6. Liu H, Ye T, Mao C (2007) Fluorescent carbon nanoparticles derived from candle soot. Angew Chem Int Ed 46:6473–6475

    Article  CAS  Google Scholar 

  7. Zhu H, Wang X, Li Y, Wang Z, Yang F, Yang X (2009) Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties. Chem Commun 45:5118–5120

    Article  Google Scholar 

  8. Li H, He X, Liu Y, Huang H, Lian S, Lee ST, Kang Z (2011) One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties. Carbon 49:605–609

    Article  CAS  Google Scholar 

  9. Zheng L, Chi Y, Dong Y, Lin J, Wang B (2009) Electrochemiluminescence of water-soluble carbon nanocrystals released electrochemically from graphite. J Am Chem Soc 131:4564–4565

    Article  CAS  Google Scholar 

  10. 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 Int Ed 52:3953–3957

    Article  CAS  Google Scholar 

  11. Liu RL, Wu D, Liu S, Koynov K, Knoll W, Li Q (2009) An aqueous route to multicolor photoluminescent carbon dots using silica spheres as carriers. Angew Chem 48:4598–4601

    Article  Google Scholar 

  12. Xu J, Sahu S, Cao L, Anilkumar P, Tackett KN II, Qian H, Bunker CE, Guliants EA, Parenzan A, Sun YP (2011) Carbon nanoparticles as chromophores for photon harvesting and photoconversion. ChemPhysChem 12:3604–3608

    Article  CAS  Google Scholar 

  13. Hu SL, Niu KY, Sun J, Yang J, Zhao NQ, Du XW (2009) One-step synthesis of fluorescent carbon nanoparticles by laser irradiation. J Mater Chem 19:484–488

    Article  CAS  Google Scholar 

  14. Hsu PC, Shih ZY, Lee CH, Chang HT (2012) Synthesis and analytical applications of photoluminescent carbon nanodots. Green Chem 14:917–920

    Article  CAS  Google Scholar 

  15. Zhou J, Sheng Z, Han H, Zou M, Li C (2012) Facile synthesis of fluorescent carbon dots using watermelon peel as a carbon source. Mater Lett 66:222–224

    Article  CAS  Google Scholar 

  16. Sahu S, Behera B, Maiti TK, Mohapatra S (2012) Simple one-step synthesis of highly luminescent carbon dots from Orange juice: application as excellent bio-imaging agents. Chem Commun 48:8835–8837

    Article  CAS  Google Scholar 

  17. Wei W, Xu C, Wu L, Wang J, Ren J, Qu X (2014) Non-enzymatic-browning-reaction: A versatile route for production of nitrogen-doped carbon dots with tunable multicolor luminescent display. Sci Rep 4:3564

    Google Scholar 

  18. Yin B, Deng J, Peng X, Long Q, Zhao J, Lu Q, Chen Q, Li H, Tang H, Zhang Y, Yao S (2013) Green synthesis of carbon dots with down-and up-conversion fluorescent properties for sensitive detection of hypochlorite with a dual-readout assay. Analyst 138:6551–6557

    Article  CAS  Google Scholar 

  19. Melhuish WH (1961) Quantum efficiencies of organic substances: effect of solvent and concentration of the fluorescent solute. J Phys Chem 65:229–235

    Article  CAS  Google Scholar 

  20. Chang L, Wu T, Chen F (2012) Determination of L-cysteine base on the reversion of fluorescence quenching of calcein by copper (II) ion. Microchim Acta 177:295–300

    Article  CAS  Google Scholar 

  21. Gao Y, Li Y, Zou X, Huang H, Su X (2012) Highly sensitive and selective detection of biothiols using graphene oxide-based “molecular beacon”-like fluorescent probe. Anal Chim Acta 731:68–74

    Article  CAS  Google Scholar 

  22. Zhang BX, Gao H, Li XL (2014) Synthesis and optical properties of nitrogen and sulfur co-doped graphene quantum dots. New J Chem 38:4615–4621

    Article  CAS  Google Scholar 

  23. Liang J, Yan J, Jaroniec M, Qiao SZ (2012) Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew Chem Int Ed 51:11496–11500

    Article  CAS  Google Scholar 

  24. Liu LQ, Li YF, Zhang L, Liu Y, Huang CZ (2011) One-step synthesis of fluorescent hydroxyls-coated carbon dots with hydrothermal reaction and its application to optical sensing of metal ions. Sci China Chem 54:1342–1347

    Article  CAS  Google Scholar 

  25. Wang W, Lu YC, Huang H, Wang AJ, Chen JR, Feng JJ (2014) Solvent-free synthesis of sulfur-and nitrogen-co-doped fluorescent carbon nanoparticles from glutathione for highly selective and sensitive detection of mercury(II) ions. Sensor Actuat B 202:741–747

    Article  CAS  Google Scholar 

  26. Wei J, Shen J, Zhang X, Guo S, Pan J, Hou X, Zhang H, Wang L, Feng B (2013) Simple one-step synthesis of water-soluble fluorescent carbon dots derived from paper ash. RSC Adv 3:13119–13122

    Article  CAS  Google Scholar 

  27. Zhou J, Yang Y, Zhang CY (2013) A low-temperature solid-phase method to synthesize highly fluorescent carbon nitride dots with tunable emission. Chem Commun 49:8605–8607

    Article  CAS  Google Scholar 

  28. Lu W, Qin X, Asiri AM, Al-Youbi AQ, Sun X (2013) Green synthesis of carbon nanodots as an effective fluorescent probe for sensitive and selective detection of mercury(II) ions. J Nanoparticle Res 15:1344–1350

    Article  Google Scholar 

  29. Lai T, Zheng E, Chen L, Wang X, Kong L, You C, Ruan Y, Weng X (2013) Hybrid carbon source for producing nitrogen-doped polymer nanodots: one-pot hydrothermal synthesis, fluorescence enhancement and highly selective detection of Fe (III). Nanoscale 5:8015–8021

    Article  CAS  Google Scholar 

  30. Zhou L, Lin Y, Huang Z, Ren J, Qu X (2012) Carbon nanodots as fluorescence probes for rapid, sensitive, and label-free detection of Hg2+ and biothiols in complex matrices. Chem Commun 48:1147–1149

    Article  CAS  Google Scholar 

  31. Zhao A, Zhao C, Li M, Ren J, Qu X (2014) Ionic liquids as precursors for highly luminescent, surface-different nitrogen-doped carbon dots used for label-free detection of Cu2+/Fe3+ and cell imaging. Anal Chim Acta 809:128–133

    Article  CAS  Google Scholar 

  32. Liu S, Tian J, Wang L, Luo Y, Zhai J, Sun X (2011) Preparation of photoluminescent carbon nitride dots from CCl4 and 1,2-ethylenediamine: a heat-treatment-based strategy. J Mater Chem 21:11726–11729

    Article  CAS  Google Scholar 

  33. Yuan C, Liu B, Liu F, Han MH, Zhang Z (2014) Fluorescence “turn on” detection of mercuric ion based on bis(dithiocarbamato)copper(II) complex functionalized carbon nnodots. Anal Chem 86:1123–1130

    Article  CAS  Google Scholar 

  34. Shang L, Yin J, Li J, Jin L, Dong S (2009) Gold nanoparticle-based near-infrared fluorescent detection of biological thiols in human plasma. Biosens Bioelectron 25:269–274

    Article  CAS  Google Scholar 

  35. Wang Q, Liu X, Zhang L, Lv Y (2012) Microwave-assisted synthesis of carbon nanodots through an eggshell membrane and their fluorescent application. Analyst 137:5392–5397

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21475113), the Sci-Tech Research Development Program of Shaanxi Province (2014JM2049), the Natural Science Foundation of Shaanxi Province (2012JQ2013), and the Special Scientific Research Funding of Xianyang Normal University (14XSYK016).

Author information

Authors and Affiliations

  1. College of Chemistry & Chemical Engineering, Xianyang Normal University, Xianyang, 712000, China

    Ying Guo, Lianli Yang, Wuwu Li, Xiaofang Wang & Yonghui Shang

  2. Key laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, 710062, China

    Baoxin Li

Authors
  1. Ying Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lianli Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wuwu Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaofang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yonghui Shang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Baoxin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Baoxin Li.

Ethics declarations

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

Electronic supplementary material

ESM 1

(DOC 1328 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, Y., Yang, L., Li, W. et al. 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, 1409–1416 (2016). https://doi.org/10.1007/s00604-016-1779-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-1779-6

Keywords

Search

Navigation