Carbon quantum dots doped with phosphorus and nitrogen are a viable fluorescent nanoprobe for determination and cellular imaging of vitamin B12 and cobalt(II)

Abstract

Phosphorus and nitrogen dually-doped carbon quantum dots (PN-CQDs) were prepared from sucrose, 85% phosphoric acid and 1,2-ethylenediamine as the sources for carbon, phosphorus and nitrogen, respectively. The PN-CQDs possess good water solubility and favorable biocompatibility. The excitation/emission peaks are at 365/451 nm, but bright blue, green, or red emissions are found depending on whether the excitation wavelengths of the laser are set to 408 nm, 488 nm, or 543 nm, respectively. Fluorescence is quenched by both vitamin B12 (VB12) and Co(II) by a combination of inner filter effect and static quenching. The PN-CQDs are shown to be useful nanoprobes for determination of VB12 and Co(II). Response to VB12 is linear in the range of 2.0–31 μM. The response to Co(II) is linear in two ranges, viz. from 1.7–12 μM and from 28 to 141 μM. The limit of detection of VB12 and Co(II) are 3.0 nM and 29.4 nM, respectively. The nanoprobe was successfully applied to the analyses of VB12 in drug samples and of Co(II) in spiked water samples, and it gave satisfactory results. The nanoprobe was also applied to the determination of VB12 and Co(II) in human hepatocarcinoma cells (type SMMC7721), human pulmonary epithelial cells (type BEAS-2B), human adenocarcinoma cells (type A549), and human pheochromocytoma cells (type PC12), respectively.

Schematic presentation of the quenching of the fluorescence of phosphorus and nitrogen dually-doped carbon quantum dots (PN-CQDs) by vitamin B12 (VB12) and Co(II).

This is a preview of subscription content, access via your institution.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. 1.

    Kumar SS, Chouhan RS, Thakur MS (2010) Trends in analysis of vitamin B12. Anal Biochem 398:139–149

    CAS  Article  Google Scholar 

  2. 2.

    Samari F, Hemmateenejad B, Rezaei Z, Shamsipur M (2012) A novel approach for rapid determination of vitamin B12 in pharmaceutical preparations using BSA-modified gold nanoclusters. Anal Methods-UK 4:4155–4160

    CAS  Article  Google Scholar 

  3. 3.

    Wang J, Wei J, Su S, Qiu J (2015) Novel fluorescence resonance energy transfer optical sensors for vitamin B12 detection using thermally reduced carbon dots. New J Chem 39:501–507

    CAS  Article  Google Scholar 

  4. 4.

    Heudi O, Kilinc T, Fontannaz P, Marley E (2006) Determination of vitamin B12 in food products and in premixes by reversed-phase high performance liquid chromatography and immunoaffinity extraction. J Chromatogr A 1101:63–68

    CAS  Article  Google Scholar 

  5. 5.

    Zhang N, Wang W, Wang K, Ding Z, Wei Z (2008) Rapid determination of vitamin B12 by inductively coupled plasma mass spectrometry in multivitamin tablets. Spectrosc Lett 41:332–336

    CAS  Article  Google Scholar 

  6. 6.

    Baker SA, Miller-Ihli NJ (2000) Determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry. Spectrochim Acta B 55:1823–1832

    Article  Google Scholar 

  7. 7.

    Jin G, Zhu Y, Jiang W, Xie B, Cheng B (1997) Spectrophotometric determination of cobalt(II) using the chromogenic reagent 4,4′-Diazobenzenediazoaminoazobenzene in a micellar surfactant medium. Analyst 122:263–265

    CAS  Article  Google Scholar 

  8. 8.

    Tomčik P, Banks CE, Davies TJ, Compton RG (2004) A self-catalytic carbon paste electrode for the detection of vitamin B12. Anal Chem 76:161–165

    Article  Google Scholar 

  9. 9.

    Gao Y, Guo F, Gokavi S, Chow A, Sheng Q, Guo M (2008) Quantification of water-soluble vitamins in milk-based infant formulae using biosensor-based assays. Food Chem 110:769–776

    CAS  Article  Google Scholar 

  10. 10.

    Gharehbaghi M, Shemirani F, Farahani MD (2009) Cold-induced aggregation microextraction based on ionic liquids and fiber optic-linear array detection spectrophotometry of cobalt in water samples. J Hazard Mater 165:1049–1055

    CAS  Article  Google Scholar 

  11. 11.

    Souza JMO, Tarley CRT (2009) Sorbent separation and enrichment method for cobalt ions determination by graphite furnace atomic absorption spectrometry in water and urine samples using multiwall carbon nanotubes. Int J Environ Sci Technol 89:489–502

    CAS  Google Scholar 

  12. 12.

    Ussher SJ, Milne A, Landing WM, Attiq-ur-Rehman K, Séguret MJM, Holland T, Achterberg EP, Nabi A, Worsfold PJ (2009) Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection. Anal Chim Acta 652:259–265

    CAS  Article  Google Scholar 

  13. 13.

    Wen X, Shi L, Wen G, Li Y, Dong C, Yang J, Shuang S (2016) Green and facile synthesis of nitrogen-doped carbon nanodots for multicolor cellular imaging and Co2+ sensing in living cells. Sensor Actuat B-Chem 235:179–187

    CAS  Article  Google Scholar 

  14. 14.

    Gong X, Li Z, Hu Q, Zhou R, Shuang S, Dong C (2017) N,S,P co-doped carbon nanodot fabricated from waste microorganism and its application for label-free recognition of manganese(VII) and L-ascorbic acid and AND logic gate operation. ACS Appl Mater Interfaces 9:38761–38772

    CAS  Article  Google Scholar 

  15. 15.

    Gong X, Zhang Q, Gao Y, Shuang S, Choi MMF, Dong C (2016) Phosphorus and nitrogen dual-doped hollow carbon dot as a nanocarrier for doxorubicin delivery and biological imaging. ACS Appl Mater Interfaces 8:11288–11297

    CAS  Article  Google Scholar 

  16. 16.

    Gupta A, Chaudhary A, Mehta P, Dwivedi C, Khan S, Verma NC, Nandi CK (2015) Nitrogen-doped, thiol-functionalized carbon dots for ultrasensitive hg(II) detection. Chem Commun 51:10750–10753

    CAS  Article  Google Scholar 

  17. 17.

    Liu X, Zhang N, Bing T, Shangguan D (2014) Carbon dots based dual-emission silica nanoparticles as a ratiometric nanosensor for Cu2+. Anal Chem 86:2289–2296

    CAS  Article  Google Scholar 

  18. 18.

    Gong X, Lu W, Paau MC, Hu Q, Wu X, Shuang S, Dong C, Choi MMF (2015) Facile synthesis of nitrogen-doped carbon dots for Fe3+ sensing and cellular imaging. Anal Chim Acta 861:74–84

    CAS  Article  Google Scholar 

  19. 19.

    Wang W, Peng J, Li F, Su B, Chen X, Chen X (2019) Phosphorus and chlorine co-doped carbon dots with strong photoluminescence as a fluorescent probe for ferric ions. Microchim Acta 186:32

    Article  Google Scholar 

  20. 20.

    Lin L, Wang Y, Xiao Y, Liu W (2019) Hydrothermal synthesis of carbon dots codoped with nitrogen and phosphorus as a turn-on fluorescent probe for cadmium(II). Microchim Acta 186:147

    Article  Google Scholar 

  21. 21.

    Sun X, Wu L, Shen J, Cao X, Wen C, Liu B, Wang H (2016) Highly selective and sensitive sensing for Al3+ and F based on green photoluminescent carbon dots. RSC Adv 6:97346–97351

    CAS  Article  Google Scholar 

  22. 22.

    Li P, Sun X, Shen J, Liu B (2016) A novel photoluminescence sensing system sensitive for and selective to bromate anions based on carbon dots. RSC Adv 6:61891–61896

    CAS  Article  Google Scholar 

  23. 23.

    Gong X, Lu W, Liu Y, Li Z, Shuang S, Dong C, Choi MMF (2015) Low temperature synthesis of phosphorous and nitrogen co-doped yellow fluorescent carbon dots for sensing and bioimaging. J Mater Chem B 3:6813–6819

    CAS  Article  Google Scholar 

  24. 24.

    Shen P, Xia Y (2014) Synthesis-modification integration: one-step fabrication of boronic acid functionalized carbon dots for fluorescent blood sugar sensing. Anal Chem 86:5323–5329

    CAS  Article  Google Scholar 

  25. 25.

    Barati A, Shamsipur M, Abdollahi H (2015) Hemoglobin detection using carbon dots as a fluorescence probe. Biosens Bioelectron 71:470–475

    CAS  Article  Google Scholar 

  26. 26.

    Liu Y, Gong X, Dong W, Zhou R, Shuang S, Dong C (2018) Nitrogen and phosphorus dual-doped carbon dots as a label-free sensor for curcumin determination in real sample and cellular imaging. Talanta 183:61–69

    CAS  Article  Google Scholar 

  27. 27.

    Wei J, Yang Y, Dong J, Wang S, Li P (2019) Fluorometric determination of pesticides and organophosphates using nanoceria as a phosphatase mimic and an inner filter effect on carbon nanodots. Microchim Acta 186:66

    Article  Google Scholar 

  28. 28.

    Hu Q, Li T, Gao L, Gong X, Rao S, Fang W, Gu R, Yang Z (2018) Ultrafast and energy-saving synthesis of nitrogen and chlorine co-doped carbon nanodots via neutralization heat for selective detection of Cr(VI) in aqueous phase. Sensors 18:3416

    Article  Google Scholar 

  29. 29.

    Xu Z, Yang L, Fan X, Jin J, Mei J, Peng W, Jiang F, Xiao Q, Liu Y (2014) Low temperature synthesis of highly stable phosphate functionalized two color carbon nanodots and their application in cell imaging. Carbon 66:351–360

    CAS  Article  Google Scholar 

  30. 30.

    Gong X, Hu Q, Paau MC, Zhang Y, Shuang S, Dong C, Choi MMF (2014) Red-green-blue fluorescent hollow carbon nanoparticles isolated from chromatographic fractions for cellular imaging. Nanoscale 6:8162–8170

    CAS  Article  Google Scholar 

  31. 31.

    Gong X, Liu Y, Yang Z, Shuang S, Zhang Z, Dong C (2017) An "on-off-on" fluorescent nanoprobe for recognition of chromium(VI) and ascorbic acid based on phosphorus/nitrogen dual-doped carbon quantum dot. Anal Chim Acta 968:85–96

    CAS  Article  Google Scholar 

  32. 32.

    Moreno P, Salvado V (2000) Determination of eight water- and fat-soluble vitamins in multi-vitamin pharmaceutical formulations by high-performance liquid chromatography. Chromatogr A 870:207–215

    CAS  Article  Google Scholar 

  33. 33.

    Vinas P, Campillo N, Lopez-Garcia I, Hernandez-Cordoba M (1996) Identification of vitamin B12 analogues by Liquid Chromatography with Electrothermal Atomic Absorption Detection. Chromatographia 42:566–557

    CAS  Article  Google Scholar 

  34. 34.

    Zu F, Yan F, Bai Z, Xu J, Wang Y, Huang Y, Zhou X (2019) The quenching of the fluorescence of carbon dots: a review on mechanisms and applications. Microchim Acta 184:1899–1914

    Article  Google Scholar 

  35. 35.

    Bai Z, Yan F, Xu J, Zhang J, Wei J, Luo Y, Chen L (2018) Dual-channel fluorescence detection of mercuric (II) and glutathione by down- and up-conversion fluorescence carbon dots. Spectrochim Acta A 205:29–39

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Science Foundation of China (No. 21705101 and 21575084), China Postdoctoral Science Foundation (No. 2018 M642969) and the Hundred Talent Programme of Shanxi Province, all of which are gratefully acknowledged. We also acknowledge Dr. Juanjuan Wang from the Scientific Instrument Center at Shanxi University for her help with LSCM measurements.

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Xiaojuan Gong or Chuan Dong.

Ethics declarations

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

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 4771 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhang, L., Wang, H., Hu, Q. et al. Carbon quantum dots doped with phosphorus and nitrogen are a viable fluorescent nanoprobe for determination and cellular imaging of vitamin B12 and cobalt(II). Microchim Acta 186, 506 (2019). https://doi.org/10.1007/s00604-019-3617-0

Download citation

Keywords

  • Carbon quantum dots
  • Nanoprobe
  • Sucrose
  • Phosphoric acid
  • 1,2-Ethylenediamine
  • Fluorescence decay times
  • Inner filter effect
  • Static quenching
  • Drug samples
  • Water samples