Skip to main content
SpringerLink
Log in

Fluorescent probe for copper(II) ion based on a rhodamine spirolactame derivative, and its application to fluorescent imaging in living cells

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

Abstract

A fluorescent probe for Cu(II) ion is presented. It is based on the rhodamine fluorophore and exhibits high selectivity and sensitivity for Cu(II) ion in aqueous methanol (2:8, v/v) at pH 7.0. The response is based on a ring opening reaction and formation of a strongly fluorescent 1:1 complex. The response is reversible and linear in the range between 50 nM and 900 nM, with a detection limit of 7.0 nM. The probe was successfully applied to fluorescent imaging of Cu(II) ions in HeLa cells.

A novel fluorescent probe 1 based on a rhodamine spirolactame derivative exhibits highly selective and sensitive recognition properties toward Cu(II) in aqueous methanol (2:8, v/v) at pH 7.0 with remarkable fluorescence enhancement and clear color change, and its high cell permeability grants its application to fluorescent imaging in living cells.

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
Scheme 2
Fig. 7

Similar content being viewed by others

References

  1. Krämer R (1998) Fluorescent probes for Cu2+ ions: fast, selective, and highly sensitive. Angew Chem Int Ed 37:772

    Article  Google Scholar 

  2. Kim BE, Nevitt T, Thiele DJ (2008) Mechanisms for copper acquisition, distribution and regulation. Nat Chem Biol 4:176

    Article  CAS  Google Scholar 

  3. Lovstad RA (2004) A kinetic study on the distribution of Cu(II)-ions between albumin and transferrin. BioMetals 17:111

    Article  CAS  Google Scholar 

  4. Luo Y, Li Y, Lv BQ, Zhou ZD, Xiao D, Choi MMF (2009) A new luminol derivative as a fluorescent probe for trace analysis of copper(II). Microchim Acta 164:411

    Article  CAS  Google Scholar 

  5. Chen HQ, Liang AN, Wang L, Liu Y, Qian BB (2009) Ultrasensitive determination of Cu2+ by synchronous fluorescence spectroscopy with functional nanoparticles. Microchim Acta 164:453

    Article  CAS  Google Scholar 

  6. Cano-Raya C, Fernández-Ramos MD, Capitán-Vallvey LF, Wolfbeis OS, Schaferling M (2005) Fluorescence quenching of the europium tetracycline hydrogen peroxide complex by copper(II) and other metal ions. Appl Spectrosc 59:1209

    Article  CAS  Google Scholar 

  7. Shao N, Zhang Y, Cheung SM, Yang RH, Chan WH, Mo T, Li KA, Liu F (2005) Copper ion-selective fluorescent sensor based on the Inner filter effect using a spiropyran derivative. Anal Chem 77:7294

    Article  CAS  Google Scholar 

  8. Turel M, Duerkop A, Yegorova A, Scripinets Y, Lobnik A, Samec N (2009) Detection of nanomolar concentrations of copper(II) with a Tb-quinoline-2-one probe using luminescence quenching or luminescence decay time. Anal Chim Acta 644:53

    Article  CAS  Google Scholar 

  9. Khatua S, Choi SH, Lee J, Huh JO, Do Y, Churchill DG (2009) Highly selective fluorescence detection of Cu2+ in water by chiral dimeric Zn2+ complexes through direct displacement. Inorg Chem 48:1799

    Article  CAS  Google Scholar 

  10. Zheng YJ, Orbulescu J, Ji XJ, Andreopoulos FM, Pham SM, Leblanc RM (2003) Development of fluorescent film sensors for the detection of divalent copper. J Am Chem Soc 125:2680

    Article  CAS  Google Scholar 

  11. Chen X, Ma H (2006) A selective fluorescence-on reaction of spiro form fluorescein hydrazide with Cu(II). Anal Chim Acta 575:217

    Article  CAS  Google Scholar 

  12. Martinez R, Zapata F, Caballero A, Espinosa A, Tárraga A, Molina P (2006) 2-Aza-1,3-butadiene derivatives featuring an anthracene or pyrene unit: highly selective colorimetric and fluorescent signaling of Cu2+ cation. Org Lett 8:3235

    Article  CAS  Google Scholar 

  13. Wen ZC, Yang R, He H, Jiang YB (2006) A highly selective charge transfer fluoroionophore for Cu2+. Chem Commun 106

  14. Zhang X, Shiraishi Y, Hiral T (2007) Cu(II)-selective green fluorescence of a rhodamine diacetic acid conjugate. Org Lett 9:5039

    Article  CAS  Google Scholar 

  15. Lee MH, Kim HJ, Yoon S, Park N, Kim JS (2008) Metal ion induced FRET off-on in tren/dansyl-appended rhodamine. Org Lett 10:213

    Article  CAS  Google Scholar 

  16. Liu JW, Lu Y (2007) A DNAzyme catalytic beacon sensor for paramagnetic Cu2+ ions in aqueous solution with high sensitivity and selectivity. J Am Chem Soc 129:9838

    Article  CAS  Google Scholar 

  17. Chen XQ, Jou MJ, Lee H, Kou SZ, Lim J, Nam SW, Park S, Kim KM, Yoon J (2009) New fluorescent and colorimetric probes bearing rhodamine and binaphthyl groups for the detection of Cu2+. Sens Actuators B 137:597

    Article  Google Scholar 

  18. Xiang Y, Tong AJ, Jin PY, Ju Y (2006) New fluorescent rhodamine hydrazone probe for Cu(II) with high selectivity and sensitivity. Org Lett 8:2863

    Article  CAS  Google Scholar 

  19. Chen XQ, Jia J, Ma HM, Wang SJ, Wang XC (2009) Characterization of rhodamine B hydroxylamide as a highly selective and sensitive fluorescence probe for copper (II). Anal Chim Acta 632:9

    Article  CAS  Google Scholar 

  20. Mei L, Xiang Y, Li N, Tong AJ (2007) A new fluorescent probe of rhodamine B derivative for the detection of copper ion. Talanta 72:1717

    Article  CAS  Google Scholar 

  21. Huo FJ, Su J, Sun YQ, Yin CX, Tong HB, Nie ZX (2010) A rhodamine-based dual probe for the visual detection of copper and the ratiometric fluorescent detection of vanadium. Dyes and Pigments 86:50

    Article  CAS  Google Scholar 

  22. Hu ZQ, Wang XM, Feng YC, Ding L, Lu HY (2011) Sulfonyl rhodamine hydrazide: A sensitive and selective chromogenic and fluorescent chemodosimeter for copper ion in aqueous media. Dyes and Pigments 88:257

    Article  CAS  Google Scholar 

  23. Zhao Y, Zhang XB, Han ZX, Qiao L, Li CY, Jian LX, Shen GL, Yu RQ (2009) Highly sensitive and selective colorimetric and off-on fluorescent probe for Cu2+ in aqueous solution and living cells. Anal Chem 81:7022

    Article  CAS  Google Scholar 

  24. Yu CW, Zhang J, Wang R, Chen LX (2010) Highly sensitive and selective colorimetric and off-on fluorescent probe for Cu2+ based on rhodamine derivative. Org Biomol Chem 8:5277

    Article  CAS  Google Scholar 

  25. Yu MX, Shi M, Chen ZG, Li FY, Li XX, Gao YH, Xu J, Yang H, Zhou ZG, Yi T, Huang CW (2008) Highly sensitive and fast responsive fluorescence turn-on chemodosimeter for Cu2+ and its application in live cell imaging. Chem Eur J 14:6892

    Article  CAS  Google Scholar 

  26. Beija M, Afonso CAM, Martinho JMG (2009) Synthesis and applications of rhodamine derivatives as fluorescent probes. Chem Soc Rev 38:2410

    Article  CAS  Google Scholar 

  27. Kim H, Lee M, Kim H, Kim J, Yoon J (2008) A new trend in rhodamine-based probes: application of spirolactam ring-opening to sensing ions. Chem Soc Rev 37:1465

    Article  CAS  Google Scholar 

  28. Liu YL, Sun Y, Du J, Lv X, Zhao Y, Chen ML, Wang P, Guo W (2011) Highly sensitive and selective turn-on fluorescent and chromogenic probe for Cu2+ and ClO− based on a N-picolinyl rhodamine B-hydrazide derivative. Org Biomol Chem 9:432

    Article  CAS  Google Scholar 

  29. Huang L, Wang X, Xie GQ, Xi PX, Li ZP, Xu M, Wu YJ, Bai DC, Zeng ZZ (2010) A new rhodamine-based chemosensor for Cu2+ and the study of its behaviour in living cells. Dalton Trans 39:7894

    Article  CAS  Google Scholar 

  30. Yang XF, Guo XQ, Zhao YB (2002) Development of a novel rhodamine-type fluorescent probe to determine peroxynitrite. Talanta 57:883

    CAS  Google Scholar 

  31. Du JJ, Fan JL, Peng XJ, Sun PP, Wang JY, Li HL, Sun SG (2010) A new fluorescent chemodosimeter for Hg2+: selectivity, sensitivity, and resistance to Cys and GSH. Org Lett 12:476

    Article  CAS  Google Scholar 

  32. Rodríguez-Cáceres MI, Agbaria RA, Warner IM (2005) Fluorescence of metal–ligand complexes of mono and di-substituted naphthalene derivatives. J Fluoresc 15:185

    Article  Google Scholar 

  33. Benesi HA, Hildebrand JH (1949) A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J Am Chem Soc 71:2703

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20975089), the Department of Science and Technology of Shandong Province of China (2008GG20005005), the Innovation Projects of the Chinese Academy of Sciences (KZCX2-EW-206), Shandong Province Doctor Fund (2008BS04031) and the 100 Talents Program of the Chinese Academy of Sciences.

Author information

Authors and Affiliations

  1. Key Laboratory of Coastal Zone Environmental Processes, CAS; Shandong Provincial Key Laboratory of Coastal Zone Environmental Processes; Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai, 264003, China

    Chunwei Yu, Jinhua Li, Ping Liu & Lingxin Chen

  2. School of Tropical and Laboratory Medicine, Hainan Medical University, Haikou, 571101, China

    Jun Zhang

  3. Department of Chemistry, Qilu Normal University, Jinan, 250013, China

    Peihai Wei

  4. Graduate University of Chinese Academy of Sciences, Beijing, 100049, China

    Chunwei Yu

Authors
  1. Chunwei Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jun Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jinhua Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ping Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Peihai Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lingxin Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lingxin Chen.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 472 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yu, C., Zhang, J., Li, J. et al. Fluorescent probe for copper(II) ion based on a rhodamine spirolactame derivative, and its application to fluorescent imaging in living cells. Microchim Acta 174, 247–255 (2011). https://doi.org/10.1007/s00604-011-0623-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-011-0623-2

Keywords

Search

Navigation