Journal of Fluorescence

, Volume 24, Issue 4, pp 1129–1136 | Cite as

A Rhodamine-Based “Off-On” Colorimetric and Fluorescent Chemosensor for Cu(II) in Aqueous and Non-aqueous Media

  • Kun Dai
  • Baolian Xu
  • Jingwen Chen


A new rhodamine derivative (RhB-NSal) bearing an electron-withdrawing group –NO2 at the 5-position of 2-hydroxyphenyl moiety was synthesized and its sensing behaviors for Cu2+ in acetonitrile and aqueous acetate-buffer/acetonitrile (2/3, v/v, pH 4.8) media were investigated. In each medium, significant absorption and fluorescence enhancements accompanied by an instant color change from colorless to pink were observed for RhB-NSal upon addition of Cu2+. RhB-NSal binds with Cu2+ forming a 1:1 stoichiometric complex with an association constant of 6.72 (±0.03) × 104 M−1 and 4.23 (±0.03) × 104 M−1, respectively. RhB-NSal displayed high selectivity for Cu2+ over possibly competitive metal ions except that Fe3+ and Bi3+ ion can respectively bring about a little interference in absorption and fluorescence with its sensing for Cu2+. In dry acetonitrile, pronounced enhancements in the absorbance and emission of RhB-NSal were induced by Cu2+, with a detection limit of 0.49 μM, exhibiting higher sensitivity than that of a known analogue bearing no substituent on its phenol ring, RhB-Sal. In aqueous solution, RhB-NSal displayed likewise a high selectivity but a lower sensitivity for Cu2+ than that in acetonitrile, with a detection limit of 14.98 μM, still more sensitive than RhB-Sal in absorption. By virtue of these properties, RhB-NSal could be used as an “Off-On” fluorescent and colorimetric chemosensor for Cu2+ in acetonitrile medium, and be developed to be a promising candidate of “Off-On” eye-naked chemosensor for Cu2+ in a weakly acidic aqueous medium.


Chemosensor Copper (II) Electronic effect Rhodamine derivative Spectroscopic response 



We thank the financial support from the Natural Science Foundation of Jiangsu Province (No. BK2012674) and from the research fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (No. AE201029).

Supplementary material

10895_2014_1393_MOESM1_ESM.doc (3 mb)
ESM 1 (DOC 2.96 MB).


  1. 1.
    Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer, New York, pp 67–69CrossRefGoogle Scholar
  2. 2.
    Beija M, Afonso CAM, Martinho JMG (2009) Synthesis and applications of rhodamine derivatives as fluorescent probes. Chem Soc Rev 38:2410–2433PubMedCrossRefGoogle Scholar
  3. 3.
    Kim HN, Lee MH, Kim HJ, Kim JS, Yoon J (2008) A new trend in rhodamine-based chemosensors: application of spirolactam ring-opening to sensing ions. Chem Soc Rev 37:1465–1472PubMedCrossRefGoogle Scholar
  4. 4.
    Goncalves MB, Dreyer J, Lupieri P, Barrera-Patino C, Ippoliti E, Webb MR, Corrie JET, Carloni P (2013) Structural prediction of a rhodamine-based biosensor and comparison with biophysical data. Phys Chem Chem Phys 15:2177–2183PubMedCrossRefGoogle Scholar
  5. 5.
    Li C-Y, Zhou Y, Li Y-F, Kong X-F, Zou C-X, Weng C (2013) Colorimetric and fluorescent chemosensor for citrate based on a rhodamine and Pb2+ complex in aqueous solution. Anal Chim Acta 774:79–84PubMedCrossRefGoogle Scholar
  6. 6.
    Wang C, Wong KM-C (2013) Selective Hg2+ sensing behaviors of rhodamine derivatives with extended conjugation based on two successive ring-opening processes. Inorg Chem 52:13432–13441PubMedCrossRefGoogle Scholar
  7. 7.
    Sasaki H, Hanaoka K, Urano Y, Terai T, Nagano T (2011) Design and synthesis of a novel fluorescence probe for Zn2+ based on the spirolactam ring-opening process of rhodamine derivatives. Bioorg Med Chem 19:1072–1078PubMedCrossRefGoogle Scholar
  8. 8.
    Sreenath K, Clark RJ, Zhu L (2012) Tricolor emission of a fluorescent heteroditopic ligand over a concentration gradient of Zinc(II) ions. J Org Chem 77:8268–8279PubMedCentralPubMedCrossRefGoogle Scholar
  9. 9.
    Park S, Kim W, Swamy KMK, Lee HY, Jung JY, Kim G, Kim Y, Kim SJ, Yoon J (2013) Rhodamine hydrazone derivatives bearing thiophene group as fluorescent chemosensors for Hg2+. Dyes Pigments 99:323–328CrossRefGoogle Scholar
  10. 10.
    Ambikapathi G, Kempahanumakkagari SK, Lamani BR, Shivanna DK, Maregowda HB, Gupta A, Malingappa P (2013) Bioimaging of peroxynitrite in MCF-7 cells by a new fluorescent probe rhodamine B phenyl hydrazide. J Fluoresc 23:705–712PubMedCrossRefGoogle Scholar
  11. 11.
    Kamal A, Kumar N, Bhalla V, Kumar M, Mahajan RK (2014) Rhodamine-dimethyliminocinnamyl based electrochemical sensors for selective detection of iron (II). Sens Actuat B: Chem 190:127–133CrossRefGoogle Scholar
  12. 12.
    Sahana A, Banerjee A, Lohar S, Sarkar B, Mukhopadhyay SK, Das D (2013) Rhodamine-based fluorescent probe for Al3+ through time-dependent PET-CHEF-FRET processes and its cell staining application. Inorg Chem 52:3627–3633PubMedCrossRefGoogle Scholar
  13. 13.
    Sun S, Qiao B, Jiang N, Wang J, Zhang S, Peng X (2014) Naphthylamine–rhodamine-based ratiometric fluorescent probe for the determination of Pd2+ ions. Org Lett 16:1132–1135PubMedCrossRefGoogle Scholar
  14. 14.
    Emrullahoğlu M, Karakuş E, Üçüncü M (2013) A rhodamine based “turn-on” chemodosimeter for monitoring gold ions in synthetic samples and living cells. Analyst 138:3638–3641PubMedCrossRefGoogle Scholar
  15. 15.
    Mahapatra AK, Manna SK, Mandal D, Mukhopadhyay CD (2013) Highly sensitive and selective rhodamine-based “off-on” reversible chemosensor for tin (Sn4+) and imaging in living cells. Inorg Chem 52:10825–10834PubMedCrossRefGoogle Scholar
  16. 16.
    Xiang Y, Tong A, Jin P, Ju Y (2006) New fluorescent rhodamine hydrazone chemosensor for Cu(II) with high selectivity and sensitivity. Org Lett 8:2863–2866PubMedCrossRefGoogle Scholar
  17. 17.
    Chereddy NR, Thennarasu S, Mandal AB (2012) A new triazole appended rhodamine chemosensor for selective detection of Cu2+ ions and live-cell imaging. Sens Actuat B: Chem 171–172:294–301CrossRefGoogle Scholar
  18. 18.
    Tang L, Guo J, Cao Y, Zhao N (2012) New application of a known molecule: Rhodamine B 8-hydroxy-2-quinolinecarboxaldehyde Schiff base as a colorimetric and fluorescent “off-on” probe for copper (II). J Fluoresc 22:1603–1608PubMedCrossRefGoogle Scholar
  19. 19.
    Mi YS, Cao Z, Chen YT, Xie QF, Xu YY, Luo YF, Shi JJ, Xiang JN (2013) Determination of trace amount of Cu2+ with a multi-responsive colorimetric and reversible chemosensor. Analyst 138:5274–5280PubMedCrossRefGoogle Scholar
  20. 20.
    Huang L, Hou F, Xi P, Bai D, Xu M, Li Z, Xie G, Shi Y, Liu H, Zeng Z (2011) A rhodamine-based “turn-on” fluorescent chemodosimeter for Cu2+ and its application in living cell imaging. J Inorg Biochem 105:800–805PubMedCrossRefGoogle Scholar
  21. 21.
    Yu C, Zhang J, Li J, Liu P, Wei P, Chen L (2011) Fluorescent probe for copper(II) ion based on a rhodamine spirolactame derivative, and its application to fluorescent imaging in living cells. Microchim Acta 174:247–255CrossRefGoogle Scholar
  22. 22.
    Wang J, Long L, Xie D, Song X (2013) Cu2+-selective “Off-On” chemosensor based on the rhodamine derivative bearing 8-hydroxyquinoline moiety and its application in live cell imaging. Sens Actuat B: Chem 177:27–33CrossRefGoogle Scholar
  23. 23.
    Sikdar A, Roy S, Haldar K, Sarkar S, Panja SS (2013) Rhodamine-based Cu2+-selective fluorosensor: synthesis, mechanism, and application in living cells. J Fluoresc 23:495–501PubMedCrossRefGoogle Scholar
  24. 24.
    Tang RR, Lei K, Chen K, Zhao H, Chen JW (2011) A rhodamine-based off-on fluorescent chemosensor for selectively sensing Cu(II) in aqueous solution. J Fluoresc 21:141–148PubMedCrossRefGoogle Scholar
  25. 25.
    Ding JH, Yuan LD, Gao L, Chen JW (2012) Fluorescence quenching of a rhodamine derivative: selectively sensing Cu2+ in acidic aqueous media. J Lumin 132:1987–1993CrossRefGoogle Scholar
  26. 26.
    Benesi HA, Hildebrand JH (1949) A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J Am Chem Soc 71:2703–2707CrossRefGoogle Scholar
  27. 27.
    Caballero A, Martínez R, Lloveras V, Ratera I, Vidal-Gancedo J, Wurst K, Tárraga A, Molina P, Veciana J (2005) Highly selective chromogenic and redox or fluorescent sensors of Hg2+ in aqueous environment based on 1,4-disubstituted azines. J Am Chem Soc 127:15666–15667PubMedCrossRefGoogle Scholar
  28. 28.
    Xu Z, Zhang L, Guo R, Xiang T, Wu C, Zheng Z, Yang F (2011) A highly sensitive and selective colorimetric and off-on fluorescent chemosensor for Cu2+ based on rhodamine B derivative. Sens Actuat B: Chem 156:546–552CrossRefGoogle Scholar
  29. 29.
    Zhang D, Wang M, Chai M, Chen X, Ye Y, Zhao Y (2012) Three highly sensitive and selective colorimetric and off-on fluorescent chemosensors for Cu2+ in aqueous solution. Sens Actuat B: Chem 168:200–206CrossRefGoogle Scholar
  30. 30.
    Yang Z, She M, Zhang J, Chen X, Huang Y, Zhu H, Liu P, Li J, Shi Z (2013) Highly sensitive and selective rhodamine Schiff base “off-on” chemosensors for Cu2+ imaging in living cells. Sens Actuat B: Chem 176:482–487CrossRefGoogle Scholar
  31. 31.
    Arbeloa IL, Ojeda PR (1981) Molecular forms of rhodamine B. Chem Phys Lett 79:347–350CrossRefGoogle Scholar
  32. 32.
    Valeur B (2001) Molecular fluorescence: principles and applications. Whiley-VCH Verlag GmbH, New York, Chapter 10CrossRefGoogle Scholar
  33. 33.
    Karakuş E, Üçüncü M, Eanes RC, Emrullahoğlu M (2013) The utilization of pH sensitive spirocyclic rhodamine dyes for monitoring D-fructose consumption during a fermentation process. New J Chem 37:2632–2635CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  1. 1.School of Chemical & Biological EngineeringYancheng Institute of TechnologyYanchengPeople’s Republic of China
  2. 2.School of Petrochemical EngineeringChangzhou UniversityChangzhouPeople’s Republic of China

Personalised recommendations