Advertisement

Analytical and Bioanalytical Chemistry

, Volume 411, Issue 16, pp 3603–3612 | Cite as

P,N Codoped carbon dots as an efficient “off-on” fluorescent probe for lipoic acid detection and its cellular dual-color imaging

  • Yuefang HuEmail author
  • Liyun LinEmail author
  • Jinfang Li
  • Jianzhi Ye
Research Paper

Abstract

A facile single hydrothermal method was developed to synthetize P,N codoped carbon dots (P,N/CDs), which show strong and stable fluorescence, good water solubility, low toxicity and good biocompatibility. Hence, a novel and efficient “off-on” P,N/CDs fluorescent probe was developed for the highly sensitive detection of lipoic acid (LA) for the first time. The fluorescence of the P,N/CDs was quenched by Cu2+ forming a P,N/CDs-Cu2+ complex, which acted as the “off” process, but Cu2+ could be removed by LA, due to stronger chelating between LA and Cu2+, forming a more stable complex, which recovered the fluorescence of the P,N/CDs, in order to achieve the “on” process. Under optimal conditions, the concentration of LA and the increased fluorescence intensity of the P,N/CDs-Cu2+ complex displayed a good linear relationship within the range of 0.05–28 μM, with a detection limit (S/N = 3) of 0.02 μM. The established “off-on” fluorescent probe was successfully applied to the analysis of LA in urine samples. The average recoveries were in the range of 98.3–101.5%, with a relative standard deviations of less than 3.1%. In addition, the P,N/CDs were also successfully applied to cellular dual-color imaging of live T24 cells. The results show that the P,N/CDs have great application potential in clinical diagnosis, bioassay and bioimaging.

Graphical abstract

Keywords

Codoped carbon dots LA detection Fluorescent probe Cell imaging 

Notes

Funding information

This study received financial support from the Natural Science Foundation of Guangxi Province (No. 2017GXNSFAA198274).

Compliance with ethical standards

Conflict of interest

The author declares that there is no conflict of interest.

Ethical standards and informed consent

The urine sample was obtained from a healthy volunteer in Hezhou University and informed consent was obtained for the use of human urine. This research was approved by Hezhou University Ethic Committee and all experiments were performed in accordance with the Guideline for Experimentation of Hezhou University.

Supplementary material

216_2019_1842_MOESM1_ESM.pdf (2.2 mb)
ESM 1 (PDF 2.17 mb)

References

  1. 1.
    Dörsam B, Fahrer J. The disulfide compound α-lipoic acid and its derivatives: a novel class of anticancer agents targeting mitochondria. Cancer Lett. 2016;371(1):12–9.Google Scholar
  2. 2.
    Zee T, Bose N, Zee J, Beck JN, Parihar J, Yang M, et al. α-Lipoic acid treatment prevents cystine urolithiasis in a mouse model of cystinuria. Nat Med. 2017;23(3):288–90.Google Scholar
  3. 3.
    Rochette L, Ghibu S, Richard C, Zeller M, Cottin Y, Vergely C. Direct and indirect antioxidant properties of α-lipoic acid and therapeutic potential. Mol Nutr Food Res. 2013;57(1):114–25.Google Scholar
  4. 4.
    Charoenkitamorn K, Chaiyo S, Chailapakul O, Siangproh W. Low-cost and disposable sensors for the simultaneous determination of coenzyme Q10 and α-lipoic acid using manganese (IV) oxide-modified screen-printed graphene electrodes. Anal Chim Acta. 2018;1004:22–31.Google Scholar
  5. 5.
    Kothari I R, Italiya K S, Sharma S, Mittal A, Chitkara D. A rapid and precise liquid chromatographic method for simultaneous determination of alpha lipoic acid and docetaxel in lipid-based Nanoformulations. J Chromatogr Sci 2018.Google Scholar
  6. 6.
    El-Enany N, Belal F, Rizk M. Spectrophotometric determination of Thioctic acid in its dosage forms through complex formation with Pd(II). J Chin Chem Soc. 2007;54:941–8.Google Scholar
  7. 7.
    Li H, Kong Y, Chang L, Feng Z, Chang N, Liu J, et al. Determination of lipoic acid in biological samples with acetonitrile–salt stacking method in CE. Chromatographia. 2014;77(1–2):145–50.Google Scholar
  8. 8.
    Yan Y, Zhang C, Gu W, Ding C, Li X, Xian Y. Facile synthesis of water-soluble WS2 quantum dots for turn-on fluorescent measurement of lipoic acid. J Phys Chem C. 2016;120(22):12170–7.Google Scholar
  9. 9.
    Sun X, Brückner C, Lei Y. One-pot and ultrafast synthesis of nitrogen and phosphorus codoped carbon dots possessing bright dual wavelength fluorescence emission. Nanoscale. 2015;7(41):17278–82.Google Scholar
  10. 10.
    Liao S, Huang X, Yang H, Chen X. Nitrogen-doped carbon quantum dots as a fluorescent probe to detect copper ions, glutathione, and intracellular pH. Anal Bioanal Chem. 2018;410(29):7701–10.Google Scholar
  11. 11.
    Chen X, Gong F, Cao Z, Zou W, Gu T. Highly cysteine-selective fluorescent nanoprobes based on ultrabright and directly synthesized carbon quantum dots. Anal Bioanal Chem. 2018;410(12):2961–70.Google Scholar
  12. 12.
    Omer KM. Highly passivated phosphorous and nitrogen codoped carbon quantum dots and fluorometric assay for detection of copper ions. Anal Bioanal Chem. 2018;410(24):6331–6.Google Scholar
  13. 13.
    Qian M, Du Y, Wang S, Li C, Jiang H, Shi W, et al. Highly crystalline multicolor carb-on Nanodots for dual-modal imaging-guided Photothermal therapy of glioma. ACS Appl Mater Interfaces. 2018;10(4):4031–40.Google Scholar
  14. 14.
    Zhao L, Li H, Xu Y, Liu H, Zhou T, Huang N, et al. Selective detection of copper ion in complex real samples based on nitrogen-doped carbon quantum dots. Anal Bioanal Chem. 2018;410:4301–9.Google Scholar
  15. 15.
    Zhu X, Zhao T, Nie Z, Miao Z, Liu Y, Yao S. Nitrogen-doped carbon nanoparticle modulated turn-on fluorescent probes for histidine detection and its imaging in living cells. Nanoscale. 2016;8(4):2205–11.Google Scholar
  16. 16.
    Singh VK, Yadav PK, Chandra S, Bano D, Kumar V, Koch B. Etal. Bright-blue-emis Sion nitrogen and phosphorus doped carbon quantum dots as a promising nanoprobe for detection of Cr (VI) and ascorbic acid in pure aqueous solution and in living cell. New J Chem. 2018;42(15):12990–7.Google Scholar
  17. 17.
    Barman MK, Jana B, Bhattacharyya S, Patra A. Photophysical properties of doped carbon dots (N, P, and B) and their influence on Electron/hole transfer in carbon dots -nickel (II) Phthalocyanine conjugates. J Phys Chem C. 2014;118(34):20034–41.Google Scholar
  18. 18.
    Ananthanarayanan A, Wang Y, Routh P, Sk MA, Than A, Lin M, et al. Nitrogen and phosphorus codoped graphene quantum dots: synthesis from adenosine triphosphate, optical properties, and cellular imaging. Nanoscale. 2015;7(17):8159–65.Google Scholar
  19. 19.
    Dikin DA, Stankovich S, Zimney EJ, Piner RD, Dommett GHB, Evmenenko G, et al. Preparation and characterization of graphene oxide paper. Nature. 2007;448(7152):457–60.Google Scholar
  20. 20.
    Hu Y, Zhang L, Li X, Liu R, Lin L, Zhao S. Green preparation of S and N codoped carbon dots from water chestnut and onion as well as their use as an off–on fluorescent probe for the quantification and imaging of coenzyme a. ACS Sustain Chem Eng. 2017;5(6):4992–5000.Google Scholar
  21. 21.
    Tan X, Li Q, Zhang X, Shen Y, Yang J. A novel and sensitive turn-on fluorescent biosensor for the determination of thioctic acid based on Cu2+-modulated N-acetyl-L-cysteine capped CdTe quantum dots. RSC Adv. 2015;5(55):44173–82.Google Scholar
  22. 22.
    Sigel H. Die hydrophoben und Metallionen-koordinierenden Eigenschaften von α-Liponsäure-ein Beispiel für intramolekulare Gleichgewichte in Metallionen-Kom plexen. Angew Chem. 1982;94(6):421–32.Google Scholar
  23. 23.
    Shi B, Su Y, Zhang LL, Huang M, Liu R, Zhao S. Nitrogen and phosphorus codoped carbon Nanodots as a novel fluorescent probe for highly sensitive detection of Fe3+ in human serum and living cells. ACS Appl Mater Interfaces. 2016;8(17):10717–25.Google Scholar
  24. 24.
    Gong Y, Yu B, Yang W, Zhang X. Phosphorus, and nitrogen codoped carbon dots as a fluorescent probe for real-time measurement of reactive oxygen and nitrogen species inside macrophages. Biosens Bioelectron. 2016;79:822–8.Google Scholar
  25. 25.
    Li H, Shao FQ, Zou SY, Yang QJ, Huang H, Feng JJ, et al. Microwave-assisted synthesis of N,P-doped carbon dots for fluorescent cell imaging. Microchim Acta. 2016;183(2):821–6.Google Scholar
  26. 26.
    Yang Z, Xu M, Liu Y, He F, Gao F, Su Y, et al. Nitrogen-doped, carbon-rich, highly photoluminescent carbon dots from ammonium citrate. Nanoscale. 2014;6:1890–5.Google Scholar
  27. 27.
    Eda G, Lin YY, Mattevi C, Yamaguchi H, Chen HA, Chen IS, et al. Blue photoluminescence from chemically derived graphene oxide. Adv Mater. 2010;22(4):505–9.Google Scholar
  28. 28.
    Sachdev A, Gopinath P. Green synthesis of multifunctional carbon dots from coriander leaves and their potential application as antioxidants, sensors and bioimaging agents. Analyst. 2015;140(12):4260–9.Google Scholar
  29. 29.
    Lai T, Zheng E, Chen L, Wang X, Kong L, You C, et al. Hybrid carbon source for producing nitrogen-doped polymer nanodots: one-pot hydrothermal synthesis, fluorescence enhancement and highly selective detection of Fe(III). Nanoscale. 2013;5(17):8015–21.Google Scholar
  30. 30.
    Zu F, Yan F, Bai Z, Xu J, Wang Y, Huang Y, et al. The quenching of the fluorescence of carbon dots: a review on mechanisms and applications. Microchim Acta. 2017;184:1899–914.Google Scholar
  31. 31.
    Hu C, Yu C, Li M, Wang X, Yang J, Zhao Z, et al. Chemically tailoring coal to Fluores-cent carbon dots with tuned size and their capacity for cu(II) detection. Small. 2014;10(23):4926–33.Google Scholar
  32. 32.
    Yan F, Shi D, Zheng T, Yun K, Zhou X, Chen L. Carbon dots as nanosensor for sensitive and selective detection of Hg2+ and l-cysteine by means of fluorescence “off-on” switching. Sensor Actuat B Chem. 2016;224:926–35.Google Scholar
  33. 33.
    Stanisavljevic M, Krizkova S, Vaculovicova M, Kizek R, Adam V. Quantum dots-fluorescence resonance energy transfer-based nanosensors and their application. Biosens Bioelectron. 2015;74:562–74.Google Scholar
  34. 34.
    Agarwalla H, Taye N, Ghorai S, Chattopadhyay S, Das A. A novel fluorescence probe for estimation of cysteine/histidine in human blood plasma and recognition of endogenous cysteine in live Hct116 cells. Chem Commun. 2014;50(69):9899–902.Google Scholar
  35. 35.
    Lou Z, Li P, Sun X, Yang S, Wang B, Han K. A fluorescent probe for rapid detection of thiols and imaging of thiols reducing repair and H2O2 oxidative stress cycles in living cells. Chem Commun. 2013;49:391–3.Google Scholar
  36. 36.
    Kostarelos K, Lacerda L, Pastorin G, Wu W, Wieckowski S, Luangsivilay J, et al. Cellular uptake of functionalized carbon nanotubes is independent of functional group and cell type. Nat Nanotechnol. 2007;2:108–13.Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Materials and Chemical engineeringHezhou UniversityHezhouChina
  2. 2.College of Chemistry and Pharmaceutical SciencesGuangxi Normal UniversityGuilinChina
  3. 3.Products Processing Research InstituteChinese Academy of Tropical Agricultural SciencesZhanjiangChina

Personalised recommendations