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Highly cysteine-selective fluorescent nanoprobes based on ultrabright and directly synthesized carbon quantum dots

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Abstract

Strongly green fluorescent carbon dots (CQDs) have been directly synthesized from 2,4-diaminophenylhydrazine and 2-hydroxy-5-methylisophthalaldehyde through a facile solvothermal method. The novel CQDs exhibit high fluorescence quantum yield and excellent water solubility due to the abundant amino and hydroxy groups on their surface. The use of the as-prepared CQDs combined with Cu2+ constructed a “turn-on” switch cysteine-responsive nanoprobe. In the CQDs-Cu2+ assemblies, the binding of Cu2+ to CQDs results in the fluorescence quenching of CQDs by electron transfer mechanism, while the addition of cysteine leads to the fluorescence recovery because of the competitive binding between cysteine and CQDs to Cu2+. The nanoprobes showed high sensitivity to cysteine with the detection limit of 2.6 nmol L−1. The selectivity investigation results demonstrated that the Cu2+-integrated nanoparticles were highly selective toward cysteine over the other amino acids and biologically related metal ions. The proposed nanoprobe was then employed for detecting the recovery of cysteine in rabbit serum and plasma samples and imaging the cysteine in cancer cells, and the recovery was found to be 98.2–104.0%. This “synthesis-modification integration” strategy for the fabrication of CQDs may offer a new sight for the preparation of multifunctional nanostructures and broadening the application of CQDs in bioimaging.

Fluorescent carbon dots (CQDs) were directly synthesized from 2,4-diaminophenylhydrazine and 2-hydroxy-5-methylisophthalaldehyde. CQDs exhibit high fluorescence quantum yield and excellent water solubility due to the abundant amino and hydroxy groups on their surface. The use of CQDs combined with Cu2+ constructed a cysteine-responsive nanoprobe, which showed high sensitivity to cysteine with the detection limit of 2.6 nM.

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References

  1. Tang J, Kong B, Wu H, Xu M, Wang Y, Zhao D, et al. Carbon nanodots featuring efficient FRET for real-time monitoring of drug delivery and two-photon imaging. Adv Mater. 2013;25:6569–74.

    Article  CAS  Google Scholar 

  2. Sasakura K, Hanaoka K, Shibuya N, Mikami Y, Kimura Y, Komatsu T, et al. Highly selective off-on fluorescent probe for histidine and its imaging in living cells. J Am Chem Soc. 2011;133:18003–5.

    Article  CAS  Google Scholar 

  3. Ding C, Zhu A, Tian Y. Functional surface engineering of C-dots for fluorescent biosensing and in vivo bioimaging. Acc Chem Res. 2014;47:20–30.

    Article  CAS  Google Scholar 

  4. Bruchez M, Moronne M, Gin P, Weiss S, Alivisatos AP. Semiconductor nanocrystals as fluorescent biological labels. Science. 1998;281:2013–6.

    Article  CAS  Google Scholar 

  5. Kim T, Canlier A, Kim GH, Choi J, Park M, Han SM. Electrostatic spray deposition of highly transparent silver nanowire electrode on flexible substrate. ACS Appl Mater Interfaces. 2013;5:788–94.

    Article  CAS  Google Scholar 

  6. Kiran K, Wan BC, Piao LH, Kim SH. Silver nanowire based flexible electrodes with improved properties: high conductivity, transparency, adhesion and low haze. Mater Res Bull. 2013;48:2944–9.

    Article  Google Scholar 

  7. Ferrari M. Cancer nanotechnology: opportunities and challenges. Nat Rev Cancer. 2005;5:161–71.

    Article  CAS  Google Scholar 

  8. Xue WJ, Yu J, Ding T, Zhang SC, Wang JG. Fast preparation of graphene using high-energy microwave vacuum radiation. J Mater Eng. 2014;5:39–43.

    Google Scholar 

  9. Zhu XL, Wu GL, Lu N, Yuan X, Li BK. A miniaturized electrochemical toxicity biosensor based on graphene oxide quantum dots/carboxylated carbon nanotubes for assessment of priority pollutants. J Hazard Mater. 2017;324:272–9.

    Article  CAS  Google Scholar 

  10. Su YJ, Xie MM, Lu XN, Wei H, Geng HJ, Yang Z, et al. Facile synthesis and photoelectric properties of carbon dots with upconversion fluorescence using arc-synthesized carbon by-products. J RSC Adv. 2014;4:4839–42.

    Article  CAS  Google Scholar 

  11. Bottini M, Balasubramanian C, Dawson MI. Isolation and characterization of fluorescent nanoparticles from pristine and oxidized electric arc-produced single-walled carbon nanotubes. J Phys Chem B. 2006;110:831–6.

    Article  CAS  Google Scholar 

  12. Bahrami M, Ranjbarian S. Production of micro- and nano-composite particles by supercritical carbon dioxide. J Supercrit Fluids. 2007;40:263–83.

    Article  CAS  Google Scholar 

  13. Chronakis IS. Novel nanocomposites and nanoceramics based on polymer nanofibers using electrospinning process: a review. J Mater Process Technol. 2005;167:283–93.

    Article  CAS  Google Scholar 

  14. Wang YF, Hu AG. Carbon quantum dots: synthesis, properties and applications. J Mater Chem C. 2014;2:6921–39.

    Article  CAS  Google Scholar 

  15. Miao YM, Li YT, Zhang ZF, Yan GQ. Turn off–on phosphorescent biosensors for detection of DNA based on quantum dots/acridine orange. Anal Biochem. 2015;475:32–9.

    Article  CAS  Google Scholar 

  16. Jiang K, Zhang L, Lu J, Xu C, Cai C, Lin H. Triple-mode emission of carbon dots: applications for advanced anti-counterfeiting. Angew Chem Int Ed. 2016;55:7231–5.

    Article  CAS  Google Scholar 

  17. Dong YQ, Wang RX, Li GL, Chen CQ, Chi YW, Chen GN. Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions. Anal Chem. 2012;84:6220–4.

    Article  CAS  Google Scholar 

  18. Wang Y, Meng Y, Wang S, Li C, Shi W, Chen J, et al. Direct solvent-derived polymer-coated nitrogen-doped carbon nanodots with high water solubility for targeted fluorescence imaging of glioma. Small. 2015;11:3575–81.

    Article  CAS  Google Scholar 

  19. Huang Q, Lin X, Zhu JJ, Tong QX. Pd-Au@carbon dots nanocomposite: facile synthesis and application as an ultrasensitive electrochemical biosensor for determination of colitoxin DNA in human serum. Biosens Bioelectron. 2017;94:507–12.

    Article  CAS  Google Scholar 

  20. Li Q, Huang Q, Zhu JJ, Ji WG, Tong QX. Carbon dots–quinoline derivative nanocomposite: facile synthesis and application as a “turn-off” fluorescent chemosensor for detection of Cu2+ ions in tap water. RSC Adv. 2016;6:87230–6.

    Article  CAS  Google Scholar 

  21. Salinas-Castillo A, Ariza-Avidad M, Pritz C, Camprubi-Robles M, Fernandez B, Ruedas-Rama MJ, et al. Carbon dots for copper detection with down and upconversion fluorescent properties as excitation sources. Chem Commun. 2013;49:1103–5.

    Article  CAS  Google Scholar 

  22. Indrajit S, Santosh KM, Fatemeh O, Enrique D, Jasleena S, Dipanjan P. Surface chemistry of carbon nanoparticles functionally select their uptake in various stages of cancer cells. Nano Res. 2017;10:3269–74.

    Article  Google Scholar 

  23. Ye L, Yong KT, Liu LW, Roy I, Hu R, Zhu J, et al. A pilot study in non-human primates shows no adverse response to intravenous injection of quantum dots. Nature Nanotech. 2012;7:453–8.

    Article  CAS  Google Scholar 

  24. Liu XJ, Zhang N, Tao B, Hang GDH. Carbon dots based dual-emission silica nanoparticles as a ratiometric nanosensor for Cu2+. Anal Chem. 2014;86:2289–96.

    Article  CAS  Google Scholar 

  25. Liu JH, Li JZ, Xu LJ, Qiao YJ, Chen JC. Facile synthesis of N, B-doped carbon dots and their application for multisensor and cellular imaging. Ind Eng Chem Res. 2017;56:3905–12.

    Article  CAS  Google Scholar 

  26. Guo L, Ge JC, Liu WM, Niu QL, Jia QY, Wang H, et al. Tunable multicolor carbon dots prepared from well-defined polythiophene derivatives and their emission mechanism. Nano. 2016;8:729–34.

    CAS  Google Scholar 

  27. Shahrokhian S. Lead phthalocyanine as a selective carrier for preparation of a cysteine-selective electrode. Anal Chem. 2001;73:5972–8.

    Article  CAS  Google Scholar 

  28. Sattarahmady N, Heli H. An electrocatalytic transducer for l-cysteine detection based on cobalt hexacyanoferrate nanoparticles with a core–shell structure. Anal Biochem. 2011;409:74–80.

    Article  CAS  Google Scholar 

  29. Aslandaş AM, Balcı M, Arık M, Şakiroğlu H, Onganer Y, Meral K. Liquid nitrogen-assisted synthesis of fluorescent carbon dots from blueberry and their performance in Fe 3+ detection. Appl Surf Sci. 2015;356:747–52.

    Article  Google Scholar 

  30. Chen XX, Jin QQ, Wu LZ, Tung CH, Tang XJ. Synthesis and unique photoluminescence properties of nitrogen-rich quantum dots and their applications. Angew Chem Int Ed. 2014;53:12542–7.

    CAS  Google Scholar 

  31. Tang Z, Lin Z, Li G, Amino HY. Nitrogen quantum dots-based nanoprobe for fluorescence detection and imaging of cysteine in biological samples. Anal Chem. 2017;89:4238–45.

    Article  CAS  Google Scholar 

  32. Li FS, Zhang YL, Li XB, Li BL, Liu YF. Biosensor of alkaline phosphatase based on non-fluorescent FRET of Eu3+-doped oxide nanoparticles and phosphorylated peptide labeled with cyanine dye. Anal Bioanal Chem. 2017;409:5491–500.

    Article  CAS  Google Scholar 

  33. Shojaeifard Z, Hemmateenejad B, Shamsipur M. Efficient on-off ratiometric fluorescence probe for cyanide ion based on perturbation of the interaction between gold nanoclusters and a copper(II)-phthalocyanine complex. Acs Appl Mater Interf. 2016;8:15177–86.

    Article  CAS  Google Scholar 

  34. Liu Y, Meng FF, Lin WY. Single fluorescent probe for reversibly detecting copper ions and cysteine in a pure water system. RSC Adv. 2016;6:30951–5.

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the National Natural Science Foundation of China (Nos. 31527803 and 21545010).

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Correspondence to Gong Fuchun or Cao Zhong.

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The authors declare that they have no competing interests.

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The authors declare that the experiments have been conducted in accordance with the protocol of the China Council on Animal Care and approved by the Animal Care Committee of China Basic Science Institute.

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Chen, X., Gong, F., Cao, Z. et al. Highly cysteine-selective fluorescent nanoprobes based on ultrabright and directly synthesized carbon quantum dots. Anal Bioanal Chem 410, 2961–2970 (2018). https://doi.org/10.1007/s00216-018-0980-3

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  • DOI: https://doi.org/10.1007/s00216-018-0980-3

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