Skip to main content

Advertisement

SpringerLink
Log in

Sensitive fluorescent light-up probe for enzymatic determination of glucose using carbon dots modified with MnO2 nanosheets

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

Abstract

We describe a highly sensitive glucose probe based on carbon dots modified with MnO2. A strong reduction of the green fluorescence of the carbon dots (CDs) happened due to the surface energy transfer (SET) from CDs to the deposited MnO2. In the presence of H2O2 (formed via enzymatic oxidation of glucose), fluorescence is restored because the MnO2 nanosheets are reduced to form colorless Mn(II) ions. These findings were used to design a fluorometric glucose assay that has a detection limit as low as 44 nM (at an S/N ratio of 3).

A strong reduction of the green fluorescence of the carbon dots (CDs) occurs due to surface energy transfer (SET) from CDs to the deposited MnO2. In the presence of H2O2 (formed by enzymatic action of glucose oxidase) the MnO2 nanosheets are reduced to form colorless Mn(II) ions, and glucose can be quantified by the fluorescence restored.

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. Zhao L, Wu G, Cai Z, Zhao T, Yao Q, Chen X (2015) Ultrasensitive non-enzymatic glucose sensing at near-neutral pH values via anodic stripping voltammetry using a glassy carbon electrode modified with Pt3Pd nanoparticles and reduced graphene oxide. Microchim Acta 182(11):2055–2060

    Article  CAS  Google Scholar 

  2. Zhao Y, Fang X, Yan X, Zhang X, Kang Z, Zhang G, Zhang Y (2015) Nanorod arrays composed of zinc oxide modified with gold nanoparticles and glucose oxidase for enzymatic sensing of glucose. Microchim Acta 182(3):605–610

    Article  CAS  Google Scholar 

  3. Pickup JC, Hussain F, Evans ND, Rolinski OJ, Birch DJ (2005) Fluorescence-based glucose sensors. Biosens Bioelectron 20(12):2555–2565

    Article  CAS  Google Scholar 

  4. Wolfbeis SO, Schäferling M, Dürkop A (2003) Reversible optical sensor membrane for hydrogen peroxide using an immobilized fluorescent probe, and its application to a glucose biosensor. Microchim Acta 143(4):221–227

    Article  CAS  Google Scholar 

  5. Aslan S, Anik Ü (2016) Microbial glucose biosensors based on glassy carbon paste electrodes modified with Gluconobacter oxydans and graphene oxide or graphene-platinum hybrid nanoparticles. Microchim Acta 183(1):73–81

    Article  CAS  Google Scholar 

  6. Devasenathipathy R, Karthik R, Chen S-M, Ali MA, Mani V, Lou B-S, Al-Hemaid FMA (2015) Enzymatic glucose biosensor based on bismuth nanoribbons electrochemically deposited on reduced graphene oxide. Microchim Acta 182(13):2165–2172

    Article  CAS  Google Scholar 

  7. Wen D, Zou X, Liu Y, Shang L, Dong S (2009) Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing. Talanta 79(5):1233–1237

    Article  CAS  Google Scholar 

  8. Li Z, Sheng L, Meng A, Xie C, Zhao K (2016) A glassy carbon electrode modified with a composite consisting of reduced graphene oxide, zinc oxide and silver nanoparticles in a chitosan matrix for studying the direct electron transfer of glucose oxidase and for enzymatic sensing of glucose. Microchim Acta 183(5):1625–1632

    Article  CAS  Google Scholar 

  9. Sodzel D, Khranovskyy V, Beni V, Turner APF, Viter R, Eriksson MO, Holtz P-O, Janot J-M, Bechelany M, Balme S, Smyntyna V, Kolesneva E, Dubovskaya L, Volotovski I, Ubelis A, Yakimova R (2015) Continuous sensing of hydrogen peroxide and glucose via quenching of the UV and visible luminescence of ZnO nanoparticles. Microchim Acta 182(9):1819–1826

    Article  CAS  Google Scholar 

  10. Wang F, Gong W, Wang L, Chen Z (2015) Enhanced amperometric response of a glucose oxidase and horseradish peroxidase based bienzyme glucose biosensor modified with a film of polymerized toluidine blue containing reduced graphene oxide. Microchim Acta 182(11):1949–1956

    Article  CAS  Google Scholar 

  11. Durán GM, Benavidez TE, Ríos Á, García CD (2016) Quantum dot-modified paper-based assay for glucose screening. Microchim Acta 183(2):611–616

    Article  Google Scholar 

  12. Shiang Y-C, Huang C-C, Chang H-T (2009) Gold nanodot-based luminescent sensor for the detection of hydrogen peroxide and glucose. Chem Commun 23:3437–3439

    Article  Google Scholar 

  13. Fang Y, Guo S, Li D, Zhu C, Ren W, Dong S, Wang E (2011) Easy synthesis and imaging applications of cross-linked green fluorescent hollow carbon nanoparticles. ACS Nano 6(1):400–409

    Article  Google Scholar 

  14. Zhu S, Tang S, Zhang J, Yang B (2012) Control the size and surface chemistry of graphene for the rising fluorescent materials. Chem Commun 48(38):4527–4539

    Article  CAS  Google Scholar 

  15. Wang D, Wang X, Guo Y, Liu W, Qin W (2014) Luminescent properties of milk carbon dots and their sulphur and nitrogen doped analogues. RSC Adv 4(93):51658–51665

    Article  CAS  Google Scholar 

  16. Li H, He X, Kang Z, Huang H, Liu Y, Liu J, Lian S, Tsang CHA, Yang X, Lee ST (2010) Water-soluble fluorescent carbon quantum dots and photocatalyst design. Angew Chem Int Ed 49(26):4430–4434

    Article  CAS  Google Scholar 

  17. Zhuo S, Shao M, Lee S-T (2012) Upconversion and downconversion fluorescent graphene quantum dots: ultrasonic preparation and photocatalysis. ACS Nano 6(2):1059–1064

    Article  CAS  Google Scholar 

  18. Guo Y, Wang D, Liu X, Wang X, Liu W, Qin W (2014) Synthesis and characterization of the nickel@ carbon dots hybrid material and its application in the reduction of Cr (VI). New J Chem 38(12):5861–5867

    Article  CAS  Google Scholar 

  19. Guo Y, Liu X, Yang C, Wang X, Wang D, Iqbal A, Liu W, Qin W (2015) Synthesis and peroxidase-like activity of cobalt@carbon-dots hybrid material. ChemCatChem 7(16):2467–2474

    Article  CAS  Google Scholar 

  20. Wang X, Wang D, Guo Y, Yang C, Iqbal A, Liu W, Qin W, Yan D, Guo H (2015) Imidazole derivative-functionalized carbon dots: using as a fluorescent probe for detecting water and imaging of live cells. Dalton Trans 44(12):5547–5554

    Article  CAS  Google Scholar 

  21. Zhao HX, Liu LQ, De Liu Z, Wang Y, Zhao XJ, Huang CZ (2011) Highly selective detection of phosphate in very complicated matrixes with an off–on fluorescent probe of europium-adjusted carbon dots. Chem Commun 47(9):2604–2606

    Article  CAS  Google Scholar 

  22. Duan N, Wu S, Dai S, Miao T, Chen J, Wang Z (2015) Simultaneous detection of pathogenic bacteria using an aptamer based biosensor and dual fluorescence resonance energy transfer from quantum dots to carbon nanoparticles. Microchim Acta 182(5):917–923

    Article  CAS  Google Scholar 

  23. Tang L, Ji R, Cao X, Lin J, Jiang H, Li X, Teng KS, Luk CM, Zeng S, Hao J (2012) Deep ultraviolet photoluminescence of water-soluble self-passivated graphene quantum dots. ACS Nano 6(6):5102–5110

    Article  CAS  Google Scholar 

  24. Shan X, Chai L, Ma J, Qian Z, Chen J, Feng H (2014) B-doped carbon quantum dots as a sensitive fluorescence probe for hydrogen peroxide and glucose detection. Analyst 139(10):2322–2325

    Article  CAS  Google Scholar 

  25. Chen Y, O’Donoghue MB, Huang Y-F, Kang H, Phillips JA, Chen X, Estevez MC, Yang CJ, Tan W (2010) A surface energy transfer nanoruler for measuring binding site distances on live cell surfaces. J Am Chem Soc 132(46):16559–16570

    Article  CAS  Google Scholar 

  26. de Mello JC, Wittmann HF, Friend RH (1997) An improved experimental determination of external photoluminescence quantum efficiency. Adv Mater 9(3):230–232

    Article  Google Scholar 

  27. O’Connor D (1984) Time-correlated single photon counting. Academic, London

    Google Scholar 

  28. Boens N, Qin W, Basaric N, Hofkens J, Ameloot M, Pouget J, Lefevre J-P, Valeur B, Gratton E, VandeVen M (2007) Fluorescence lifetime standards for time and frequency domain fluorescence spectroscopy. Anal Chem 79(5):2137–2149

    Article  CAS  Google Scholar 

  29. Wang D, Guo Y, Liu W, Qin W (2014) Preparation and photoluminescent properties of magnetic Ni@ SiO 2–CDs fluorescent nanocomposites. RSC Adv 4(15):7435–7439

    Article  CAS  Google Scholar 

  30. Qu S, Wang X, Lu Q, Liu X, Wang L (2012) A biocompatible fluorescent ink based on water-soluble luminescent carbon nanodots. Angew Chem 124(49):12381–12384

    Article  Google Scholar 

  31. Hu L, Chen W, Xie X, Liu N, Yang Y, Wu H, Yao Y, Pasta M, Alshareef HN, Cui Y (2011) Symmetrical MnO2–carbon nanotube–textile nanostructures for wearable pseudocapacitors with high mass loading. ACS Nano 5(11):8904–8913

    Article  CAS  Google Scholar 

  32. Sui N, Duan Y, Jiao X, Chen D (2009) Large-scale preparation and catalytic properties of one-dimensional α/β-MnO2 nanostructures. J Phys Chem C 113(20):8560–8565

    Article  CAS  Google Scholar 

  33. Devaraj S, Munichandraiah N (2008) Effect of crystallographic structure of MnO2 on its electrochemical capacitance properties. J Phys Chem C 112(11):4406–4417

    Article  CAS  Google Scholar 

  34. Nakayama M, Sato A, Yamaguchi R (2013) Decomposition and detection of hydrogen peroxide using δ-MnO2 thin film electrode with self-healing property. Electroanalysis 25(10):2283–2288

    CAS  Google Scholar 

  35. Yuan J, Cen Y, Kong X-J, Wu S, Liu C-L, Yu R, Chu X (2015) MnO2-nanosheet-modified upconversion nanosystem for sensitive turn-on fluorescence detection of H2O2 and glucose in blood. ACS Appl Mater Interfaces 7:10548–10555

    Article  CAS  Google Scholar 

  36. Yonzon CR, Haynes CL, Zhang X, Walsh JT, Van Duyne RP (2004) A glucose biosensor based on surface-enhanced Raman scattering: improved partition layer, temporal stability, reversibility, and resistance to serum protein interference. Anal Chem 76(1):78–85

    Article  CAS  Google Scholar 

  37. Tang B, Cao L, Xu K, Zhuo L, Ge J, Li Q, Yu L (2008) A new nanobiosensor for glucose with high sensitivity and selectivity in serum based on fluorescence resonance energy transfer (FRET) between CdTe quantum dots and Au nanoparticles. Chem Eur J 14(12):3637–3644

    Article  CAS  Google Scholar 

  38. Salimi A, Compton RG, Hallaj R (2004) Glucose biosensor prepared by glucose oxidase encapsulated sol-gel and carbon-nanotube-modified basal plane pyrolytic graphite electrode. Anal Biochem 333(1):49–56

    Article  CAS  Google Scholar 

  39. Jin L, Shang L, Guo S, Fang Y, Wen D, Wang L, Yin J, Dong S (2011) Biomolecule-stabilized Au nanoclusters as a fluorescence probe for sensitive detection of glucose. Biosens Bioelectron 26(5):1965–1969

    Article  CAS  Google Scholar 

  40. Wang J (2008) Electrochemical glucose biosensors. Chem Rev 108(2):814–825

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors would like to thank the Natural Science Foundation of China (no. 21271094). This work was supported by the Gansu Province Natural Science Foundation of China (Grant no. 1508RJZA078).

Author information

Authors and Affiliations

  1. Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, People’s Republic of China

    Hong Ma, Xiaoyu Liu, Xudong Wang, Xinran Li, Chengduan Yang, Anam Iqbal, Weisheng Liu & Wenwu Qin

  2. College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, People’s Republic of China

    Xiaoyu Liu

  3. Lanzhou University Hospital, Lanzhou, 730000, People’s Republic of China

    Jiping Li

Authors
  1. Hong Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaoyu Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xudong Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xinran Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Chengduan Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Anam Iqbal
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Weisheng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jiping Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Wenwu Qin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Wenwu Qin.

Ethics declarations

The authors declare that they have no competing interests.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 1217 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ma, H., Liu, X., Wang, X. et al. Sensitive fluorescent light-up probe for enzymatic determination of glucose using carbon dots modified with MnO2 nanosheets. Microchim Acta 184, 177–185 (2017). https://doi.org/10.1007/s00604-016-2004-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-016-2004-3

Keywords

Search

Navigation