Skip to main content
Log in

Nitrogen-doped carbon quantum dots as a fluorescence probe combined with magnetic solid-phase extraction purification for analysis of folic acid in human serum

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

Abstract

A novel and sensitive method based on nitrogen-doped carbon quantum dots as a fluorescence probe coupled with magnetic solid-phase extraction (MSPE) purification for analysis of folic acid (FA) in human serum samples has been established for the first time. In the developed system, magnetic nanoparticles coated with hexanoic acid (Fe3O4@C6) were synthesized by a one-step chemical co-precipitation method with good magnetic properties and dispersibility for sample purification, and it is better to be separated from the sample. High fluorescence nitrogen-doped carbon quantum dots (N-CQDs), simply prepared using a one-step hydrothermal method with nitrilotriacetic acid, could be selectively quenched by FA. Based on this phenomenon, a fluorescence assay was proposed for specific determination of FA. Various operational experiment parameters have been studied and optimized in detail. Under the optimum experimental conditions, the detection limit of the proposed method for FA was evaluated to be 0.5 nM (S/N = 3), while the relative standard deviation (RSD) was 1.2% (n = 6). Finally, the proposed method was applied for determination of trace levels of FA from human serum samples and quantitative recoveries were achieved within the range of 95.7–103.5%. All of the results showed that the proposed method had significant application in further research.

Schematic of synthesis of N-CQDs and schematic of suggested mode for analysis of folic acid (FA).

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

Access this article

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

Instant access to the full article PDF.

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

Similar content being viewed by others

References

  1. Quaglia M, Chenon K, Hall AJ, De LE, Sellergren B. Target analogue imprinted polymers with affinity for folic acid and related compounds. J Am Chem Soc. 2001;123(10):2146.

    Article  CAS  Google Scholar 

  2. Kalimuthu P, John SA. Selective electrochemical sensor for folic acid at physiological pH using ultrathin electropolymerized film of functionalized thiadiazole modified glassy carbon electrode. Biosens Bioelectron. 2009;24(12):3575–80.

    Article  CAS  Google Scholar 

  3. Dai H, Li Y, Zhang S, Gong L, Li X, Lin Y. Delicate photoelectrochemical sensor for folic acid based on carbon nanohorns supported interwoven titanate nanotubes. Sensor Actuat B Chem. 2016;222:120–6.

    Article  CAS  Google Scholar 

  4. Xiao F, Ruan C, Liu L, Yan R, Zhao F, Zeng B. Single-walled carbon nanotube-ionic liquid paste electrode for the sensitive voltammetric determination of folic acid. Sensor Actuat B Chem. 2008;134(2):895–901.

    Article  CAS  Google Scholar 

  5. Lermo A, Fabiano S, Hernandez S, Galve R, Marco M, Alegret S, et al. Immunoassay for folic acid detection in vitamin-fortified milk based on electrochemical magneto sensors. Biosens Bioelectron. 2009;24(7):2057–63.

    Article  CAS  Google Scholar 

  6. Zhu Z, Wu H, Wu S, Huang Z, Zhu Y, Xi L. Determination of methotrexate and folic acid by ion chromatography with electrochemical detection on a functionalized multi-wall carbon nanotube modified electrode. J Chromatogr A. 2013;1283(6):62–7.

    Article  CAS  Google Scholar 

  7. Prasad BB, Madhuri R, Tiwari MP, Sharma PS. Electrochemical sensor for folic acid based on a hyperbranched molecularly imprinted polymer-immobilized sol–gel-modified pencil graphite electrode. Sensor Actuat B Chem. 2010;146(1):321–30.

    Article  CAS  Google Scholar 

  8. Rao GR, Kanjilal G, Mohan KR. Extended application of Folin-Ciocalteu reagent in the determination of drugs. Analyst. 1978;103(1230):993–4.

    Article  CAS  Google Scholar 

  9. Rui ASL, Lima JFC, Reis BF, Santos JLM, Zagatto EAG. Photochemical-fluorimetric determination of folic acid in a multicommutated flow system. Anal Chim Acta. 1997;351(1):223–8.

    Google Scholar 

  10. Zhang BT, Zhao L, Lin JM. Determination of folic acid by chemiluminescence based on peroxomonosulfate-cobalt(II) system. Talanta. 2008;74(5):1154–9.

    Article  CAS  Google Scholar 

  11. Lebiedzińska A, DąBrowska M, Szefer P, Marszałł M. High-performance liquid chromatography method for the determination of folic acid in fortified food products. Toxicol Mech Methods. 2008;18(6):463–7.

    Article  Google Scholar 

  12. Wang H, Lu Q, Hou Y, Liu Y, Zhang Y. High fluorescence S,N co-doped carbon dots as an ultra-sensitive fluorescent probe for the determination of uric acid. Talanta. 2016;155:62–9.

    Article  CAS  Google Scholar 

  13. Deng X, Guo Q, Chen X, Xue T, Wang H, Yao P. Rapid and effective sample clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography–mass spectrometry. Food Chem. 2014;145(7):853.

    Article  CAS  Google Scholar 

  14. Pan SD, Chen XH, Shen HY, Li XP, Cai MQ, Zhao YG, et al. Rapid and effective sample cleanup based on graphene oxide-encapsulated core-shell magnetic microspheres for determination of fifteen trace environmental phenols in seafood by liquid chromatography-tandem mass spectrometry. Anal Chim Acta. 2016;919:34–46.

    Article  CAS  Google Scholar 

  15. Shamsipur M, Rajabi HR. Pure zinc sulfide quantum dot as highly selective luminescent probe for determination of hazardous cyanide ion. Mat Sci Eng C-Mater. 2014;36(1):139–45.

    Article  CAS  Google Scholar 

  16. Rajabi HR, Shamsipur M, Khosravi AA, Khani O, Yousefi MH. Selective spectrofluorimetric determination of sulfide ion using manganese doped ZnS quantum dots as luminescent probe. Spectrochim Acta A. 2013;107(7):256–62.

    Article  CAS  Google Scholar 

  17. Mewada A, Pandey S, Thakur M, Jadhav D, Sharon M. Swarming carbon dots for folic acid mediated delivery of doxorubicin and biological imaging. J Mater Chem B. 2014;2(6):698–705.

    Article  CAS  Google Scholar 

  18. Heinrichs RW, Ammari N. Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions. Anal Chem. 2012;84(14):6220.

    Article  Google Scholar 

  19. Zhang YL, Wang L, Zhang HC, Liu Y, Wang HY, Kang ZH, et al. Graphitic carbon quantum dots as a fluorescent sensing platform for highly efficient detection of Fe3+ ions. RSC Adv. 2013;3(11):3733–8.

    Article  CAS  Google Scholar 

  20. Simões EFC, Leitão JMM, Esteves da Silva JCG. Carbon dots prepared from citric acid and urea as fluorescent probes for hypochlorite and peroxynitrite. Microchim Acta. 2016;183(5):1769–77.

    Article  Google Scholar 

  21. Chen H, Li W, Zhao P, Nie Z, Yao S. A CdTe/CdS quantum dots amplified graphene quantum dots anodic electrochemiluminescence platform and the application for ascorbic acid detection in fruits. Electrochim Acta. 2015;178:407–13.

    Article  CAS  Google Scholar 

  22. Kim SRA, Jongsung. Selective detection of dopamine in the presence of ascorbic acid via fluorescence quenching of InP/ZnS quantum dots. Int J Nanomedicine. 2015;10(Spec Iss):113.

    Google Scholar 

  23. Zhang H, Chen Y, Liang M, Xu L, Qi S, Chen H, et al. Solid-phase synthesis of highly fluorescent nitrogen-doped carbon dots for sensitive and selective probing ferric ions in living cells. Anal Chem. 2014;86(19):9846.

    Article  CAS  Google Scholar 

  24. Shen LM, Liu J. New development in carbon quantum dots technical applications. Talanta. 2016;156-157:245.

    Article  CAS  Google Scholar 

  25. Chen J, Liu J, Li J, Xu L, Qiao Y. One-pot synthesis of nitrogen and sulfur co-doped carbon dots and its application for sensor and multicolor cellular imaging. J Colloid Interf Sci. 2017;485:167–74.

    Article  Google Scholar 

  26. Zhu L, Xu G, Song Q, Tang T, Wang X, Wei F, et al. Highly sensitive determination of dopamine by a turn-on fluorescent biosensor based on aptamer labeled carbon dots and nano-graphite. Sensor Actuat B Chem. 2016;231:506–12.

    Article  CAS  Google Scholar 

  27. Cheng G, He M, Peng H, Hu B. Dithizone modified magnetic nanoparticles for fast and selective solid phase extraction of trace elements in environmental and biological samples prior to their determination by ICP-OES. Talanta. 2012;88(1):507.

    Article  CAS  Google Scholar 

  28. Chen J, Zhu X. Magnetic solid phase extraction using ionic liquid-coated core-shell magnetic nanoparticles followed by high-performance liquid chromatography for determination of Rhodamine B in food samples. Food Chem. 2016;200:10–5.

    Article  CAS  Google Scholar 

  29. He Y, Li N, Ma JJ. Magnetic solid-phase extraction clean-up combined with solidified floating organic drop microextraction for determination of trace mercury (II) in tea samples. J Chem Soc Pakistan. 2014;36(6):1162–8.

    CAS  Google Scholar 

  30. Henry B. Preparation and characterization of graphene quantum dots-Fe3O4 nanocomposite as an efficient adsorbent in magnetic solid phase extraction: application to determination of bisphenol A in water samples. Anal Methods. 2014;6(20):8413–9.

    Article  Google Scholar 

  31. Liao W, Ma Y, Chen A, Yang Y. Preparation of fatty acids coated Fe3O4 nanoparticles for adsorption and determination of benzo(a)pyrene in environmental water samples. Chem Eng J. 2015;271:232–9.

    Article  CAS  Google Scholar 

  32. Liu Y, Zhao Y, Zhang Y. One-step green synthesized fluorescent carbon nanodots from bamboo leaves for copper(II) ion detection. Sensor Actuat B Chem. 2014;196(2):647–52.

    Article  CAS  Google Scholar 

  33. Li W, Zhang Z, Kong B, Feng S, Wang J, Wang L, et al. Simple and green synthesis of nitrogen-doped photoluminescent carbonaceous nanospheres for bioimaging. Angew Chem Int Ed Engl. 2013;52(31):8151–815.

    Article  CAS  Google Scholar 

  34. Huang H, Li C, Zhu S, Wang H, Chen C, Wang Z, et al. Histidine-derived nontoxic nitrogen-doped carbon dots for sensing and bioimaging applications. Langmuir. 2014;30(45):13542–8.

    Article  CAS  Google Scholar 

  35. Liao J, Cheng Z, Zhou L. Nitrogen-doping enhanced fluorescent carbon dots: green synthesis and their applications for bioimaging and label-free detection of Au3+ ions. ACS Sustain Chem Eng. 2016;4(6):3053–61.

    Article  CAS  Google Scholar 

  36. Wang R, Wang X, Sun Y. One-step synthesis of self-doped carbon dots with highly photoluminescence as multifunctional biosensors for detection of iron ions and pH. Sensor Actuat B Chem. 2016;241:73–9.

    Article  Google Scholar 

  37. Li X, Chen L. Fluorescence probe based on amino-functionalized fluorescent magnetic nanocomposite for detection of folic acid in serum. ACS Appl Mater Inter. 2016;8:46.

    Google Scholar 

  38. Arvand M, Dehsaraei M. A simple and efficient electrochemical sensor for folic acid determination in human blood plasma based on gold nanoparticles-modified carbon paste electrode. Mat Sci Eng C. 2013;33(6):3474.

    Article  CAS  Google Scholar 

  39. Aurora-Prado MS, Silva CA, Tavares MFM, Altria KD. Determination of folic acid in tablets by microemulsion electrokinetic chromatography. J Chromatogr A. 2004;1051(1–2):291–6.

    Article  CAS  Google Scholar 

  40. Geszke-Moritz M, Clavier G, Lulek J, Schneider R. Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media. J Lumin. 2012;132(4):987–91.

    Article  CAS  Google Scholar 

Download references

Funding information

The work was strongly supported by the Analysis and Testing Foundation of Kunming University of Science and Technology.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yaling Yang.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Ethical approval

Informed consent was obtained from all individual participants serum samples were collected from. The studies have been approved by Kunming University of Science and Technology Ethics Committee and Carnegie Mellon University Ethics Committee and have been performed in accordance with the ethical standards.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, M., Jiao, Y., Cheng, C. et al. Nitrogen-doped carbon quantum dots as a fluorescence probe combined with magnetic solid-phase extraction purification for analysis of folic acid in human serum. Anal Bioanal Chem 409, 7063–7075 (2017). https://doi.org/10.1007/s00216-017-0665-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-017-0665-3

Keywords

Navigation