Skip to main content
SpringerLink
Log in

New fluorescent sensor based on a calix[4]arene bearing two triazole–coumarin units for copper ions: application for Cu2+ detection in human blood serum

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

A novel fluorescent chemosensor calix[4]arene L, containing two fluorogenic coumarin units at the lower rim has been synthesized via click reaction. The structure of this chemosensor, was characterized by IR, NMR spectra and elemental analysis. Ion-binding properties of L were investigated in acetonitrile with different metal ions and the recognition process was monitored by fluorescence, UV-Vis and 1H NMR spectral changes. In comparison with other metal ions, chemosensor L showed a specific selectivity toward copper ions‏. The Job plot analysis revealed that the binding between L with Cu2+ is in 1:1 stoichiometry. The association constant (Ka) for the complex L.Cu2+ was found to be 1.6 × 105 M−1. The limit of detection of the sensor L was determined to be 5.4 × 10−7 M. This sensitive and selective chemosensor was successfully applied for the detection of Cu2+ ions in human blood serum with 90–100% recovery.

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

Similar content being viewed by others

References

  1. Cowan, J.A.: Inorganic Biochemistry: An Introduction. Wiley, New York (1997)

    Google Scholar 

  2. Flora, S.J.S., Mittal, M., Mehta, A.: Heavy metal induced oxidative stress & its possible reversal by chelation therapy. Indian J. Med. Res. 128, 501–523 (2008)

    CAS  PubMed  Google Scholar 

  3. Sutariya, P.G., Pandya, A., Lodhab, A., Menon, S.K.: Fluorescence switch on-off-on receptor constructed of quinoline allied calix[4]arene for selective recognition of Cu2+ from blood serum and F– from industrial waste water. Analyst 138, 2531–2535 (2013)

    Article  CAS  PubMed  Google Scholar 

  4. Barceloux, D.G.: Copper. J. Toxicol. Clin. Toxicol. 37, 217–230 (1999)

    Article  CAS  PubMed  Google Scholar 

  5. Zhang, X.B., Peng, J., He, C.L., Shen, G.L., Yu, R.Q.: A highly selective fluorescent sensor for Cu2+ based on 2-(2′-hydroxyphenyl) benzoxazole in a poly (vinyl chloride) matrix. Anal. Chim. Acta 567, 189–195 (2006)

    Article  CAS  Google Scholar 

  6. Que, E.L., Domaille, D.W., Chang, C.J.: Metals in neurobiology: probing their chemistry and biology with molecular imaging. Chem. Rev. 108, 1517–1549 (2008)

    Article  CAS  PubMed  Google Scholar 

  7. Georgopoulos, P.G., Roy, A., Yonone-Lioy, M.J., Opiekun, R.E., Lioy, P.J.: Environmental copper: its dynamics and human exposure issues. J. Toxicol. Environ. Health B. 4, 341–394 (2001)

    Article  CAS  Google Scholar 

  8. Gaetke, L.M., Ching, K.C.: Copper toxicity, oxidative stress, and antioxidant nutrients. Toxicology 189, 147–163 (2003)

    Article  CAS  PubMed  Google Scholar 

  9. Valeur, B., Leray, I.: Design principles of fluorescent molecular sensors for cation recognition. Coord. Chem. Rev. 205, 3–40 (2000)

    Article  CAS  Google Scholar 

  10. De Silva, A.P., Gunaratne, H.Q.N., Gunnlaugsson, T., Huxley, J.M., Mchoy, C.P., Rademacher, J.T., Rice, T.E.: Signaling recognition events with fluorescent sensors and switches. Chem. Rev. 97, 1515–1566 (1997)

    Article  PubMed  Google Scholar 

  11. Beer, P.D., Gale, P.A.: Anion recognition and sensing: the state of the art and future perspectives. Angew. Chem. Int. Ed. 40, 486–516 (2001)

    Article  CAS  Google Scholar 

  12. Beer, P.D., Hayes, E.J.: Transition metal and organometallic anion complexation agents. Coord. Chem. Rev. 240, 167–189 (2003)

    Article  CAS  Google Scholar 

  13. Kim, J.S., Quang, D.T.: Calixarene-derived fluorescent probes. Chem. Rev. 107, 3780–3799 (2007)

    Article  CAS  PubMed  Google Scholar 

  14. Rurack, K., Genger, U.R.: Rigidization, preorientation and electronic decoupling—the ‘magic triangle’ for the design of highly efficient fluorescent sensors and switches. Chem. Soc. Rev. 31, 116–127 (2002)

    Article  CAS  PubMed  Google Scholar 

  15. Maity, D., Chakraborty, A., Gunupuru, R., Paul, P.: Calix[4]arene based molecular sensors with pyrene as fluoregenic unit: effect of solvent in ion selectivity and colorimetric detection of fluoride. Inorg. Chim. Acta. 372, 126–135 (2011)

    Article  CAS  Google Scholar 

  16. Xu, Z., Kim, S., Kim, H.N., Han, S.J., Lee, C., Kim, J.S., Qian, X., Yoon, J.: A naphthalimide–calixarene as a two-faced and highly selective fluorescent chemosensor for Cu2+ or F–. Tetrahedron Lett. 48, 9151–9154 (2007)

    Article  CAS  Google Scholar 

  17. Joseph, R., Ramanuja, B., Acharya, A., Rao, C.P.: Fluorescence switch-on sensor for Cu2+ by an amide linked lower rim 1, 3-bis (2-picolyl) amine derivative of calix [4] arene in aqueous methanol. Tetrahedron Lett. 50, 2735–2739 (2009)

    Article  CAS  Google Scholar 

  18. Li, G.K., Xu, Z.X., Chen, C.F., Huang, Z.T.: A highly efficient and selective turn-on fluorescent sensor for Cu2+ ion based on calix[4]arene bearing four iminoquinoline subunits on the upper rim. Chem. Commun. 15, 1774–1776 (2008)

    Article  CAS  Google Scholar 

  19. Ma, H., Ma, Q., Su, M., Nie, L., Han, H., Xiong, S., Xin, B., Liu, G.: Detection of trace Cu II by a designed calix[4]arene based fluorescent reagent. New J. Chem. 26, 1456–1460 (2002)

    Article  CAS  Google Scholar 

  20. Rebek, J.r.: Host–guest chemistry of calixarene capsules. Chem. Commun. 8, 637–643 (2000)

    Article  Google Scholar 

  21. Webber, P.R.A., Cowley, A., Drew, M.G.B.: Potassium selective calix[4] semitubes. Chem. Eur. J. 9, 2439–2446 (2003)

    Article  CAS  PubMed  Google Scholar 

  22. Dhir, A., Bhalla, V., Kumar, M.: Ratiometric sensing of Hg2+ based on the calix[4]arene of partial cone conformation possessing a dansyl moiety. Org. Lett. 10, 4891–4894 (2008)

    Article  CAS  PubMed  Google Scholar 

  23. Malval, J.P., Leray, I., Valeur, B.: A highly selective fluorescent molecular sensor for potassium based on a calix[4]bisazacrown bearing boron-dipyrromethene fluorophores. New J. Chem. 29, 1089–1094 (2005)

    Article  CAS  Google Scholar 

  24. Chawla, H.M., Sahu, S.N., Shrivastava, R.: A novel calix[4]arene-based neutral semicarbazone receptor for anion recognition. Tetrahedron Lett. 48, 6054–6058 (2007)

    Article  CAS  Google Scholar 

  25. Kolb, H.C., Finn, M.G., Sharpless, K.B.: Click chemistry: diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 40, 2004–2021 ‏(2001)

    Article  CAS  Google Scholar 

  26. Song, M., Sun, Z., Han, C., Tian, D., Li, H., Kim, J.S.: Calixarene-based chemosensors by means of click chemistry. Chem. Asian. J. 9, 2344–2357 (2014)

    Article  CAS  PubMed  Google Scholar 

  27. Maity, D., Govindaraju, T.: Highly selective colorimetric chemosensor for Co2+. Inorg. Chem. 50, 11282–11284 (2011)

    Article  CAS  PubMed  Google Scholar 

  28. Secor, K.E., Glass, T.E.: Selective amine recognition: development of a chemosensor for dopamine and norepinephrine. Org. Lett. 6, 3727–3730 (2004)

    Article  CAS  PubMed  Google Scholar 

  29. Yan, M.H., Li, T.R., Yang, Z.Y.: A novel coumarin Schiff-base as a Zn (II) ion fluorescent sensor. Inorg. Chem. Commun. 14, 463–465 (2011)

    Article  CAS  Google Scholar 

  30. Bekhradnia, A.R., Domehri, E., Khosravi, M.: Novel coumarin-based fluorescent probe for selective detection of Cu(II). Spectrochim. Acta A 152, 18–22 (2016)

    Article  CAS  Google Scholar 

  31. Hosseinzadeh, R., Nemati, M., Zadmard, R., Mohadjerani, M.: Amidofluorene-appended lower rim 1, 3-diconjugate of calix[4]arene: synthesis, characterization and highly selective sensor for Cu2+. Beilstein J. Org. Chem. 12, 1749–1757 (2016)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  32. Chalmardi, G.B., Tajbakhsh, M., Bekhradnia, A.R., Hosseinzadeh, R.: A highly sensitive and selective novel fluorescent chemosensor for detection of Cr3+ based on a Schiff base. Inorg. Chim. Acta. 462, 241–248 (2017)

    Article  CAS  Google Scholar 

  33. Tajbakhsh, M., Chalmardi, G.B., Bekhradnia, A.R., Hosseinzadeh, R., Hasani, N., Amiri, M.R.A.: A new fluorene-based Schiff-base as fluorescent chemosensor for selective detection of Cr3+ and Al3+. Spectrochim. Acta A 189, 22–31 (2018)

    Article  CAS  Google Scholar 

  34. Li, Z.T., Ji, G.Z., Zhao, C.X., Yuan, S.D., Ding, H., Huang, C., Du, A.L., Wei, M.: Self-assembling calix[4]arene [2]catenanes. preorganization, conformation, selectivity, and efficiency. J. Org. Chem. 64, 3572–3584 (1999)

    Article  CAS  PubMed  Google Scholar 

  35. Ivana, K., Pavol, K.: Synthesis of novel coumarin based fluorescent probes. Collect. Czech. Chem. Commun. 72, 996–1004 (2007)

    Article  CAS  Google Scholar 

  36. Ho, I.T., Haung, K.C., Chung, W.S.: 1,3-Alternate calix[4]arene as a homobinuclear ditopic fluorescent chemosensor for Ag+ ions. Chem. Asian. J. 6, 2738–2746 (2011)

    Article  CAS  PubMed  Google Scholar 

  37. Choi, M., Kim, M., Lee, K.D., Han, K.N., Yoon, I.A., Chung, H.J., Yoon, J.: A new reverse PET chemosensor and its chelatoselective aromatic cadmiation. Org. Lett. 3, 3455–3457 (2001)

    Article  CAS  PubMed  Google Scholar 

  38. Kim, S.K., Lee, J.K., Lim, J.M., Kim, J.W., Kim, J.S.: Pb2+ sensing chemo-sensor: thiacalix[4]crown-based lumino-ionophore. Bull. Korean Chem. Soc. 25, 1247–1250 (2004)

    Article  CAS  Google Scholar 

  39. Chae, M.Y., Cherian, X.M., Czarnik, A.W.: New reagents for the syntheses of fluorescent chemosensors. Anthrylogous ethylene dibromides. J. Org. Chem. 58, 5797–5801 (1993)

    Article  CAS  Google Scholar 

  40. Li, Y., Zhang, X., Zhu, B., Yan, J., Xu, W.: A highly selective colorimetric and “off-on-off” fluorescent probe for fluoride ions. Anal. Sci. 26, 1077–1080 (2010)

    Article  CAS  PubMed  Google Scholar 

  41. Ma, Q.J., Zhang, X.B., Zhao, X.H., Jin, Z., Mao, G.J., Shen, G.L., Yu, R.Q.: A highly selective fluorescent probe for Hg2+ based on a rhodamine–coumarin conjugate. Anal. Chim. Acta 663, 85–90 (2010)

    Article  CAS  PubMed  Google Scholar 

  42. Benesi, H.A., Hildebrand, J.H.J.: A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J. Am. Chem. Soc. 71, 2703–2707 (1949)

    Article  CAS  Google Scholar 

  43. Li, Z.Y., Su, H.K., Tong, H.X., Yin, Y., Xiao, T., Sun, X.Q., Wang, L., et al.: Calix [4] arene containing thiourea and coumarin functionality as highly selective fluorescent and colorimetric chemosensor for fluoride ion. Spectrochim. Acta A 200, 307–312 (2018)

    Article  CAS  Google Scholar 

  44. Chawla, H.M., Goel, P., Shukla, R.: Calix [4] arene based molecular probe for sensing copper ions. Tetrahedron Lett. 55, 2173–2176 (2014)

    Article  CAS  Google Scholar 

  45. Quang, D.T., Jung, H.S., Yoon, J.H., Lee, S.Y., Kim, J.S.: Coumarin appended calix [4] arene as a selective fluorometric sensor for Cu2+ ion in aqueous solution. Bull. Korean Chem. Soc. 28, 682–684 (2007)

    Article  CAS  Google Scholar 

  46. Chawla, H.M., Munjal, P., Goel, P.: Synthesis and evaluation of a new colorimetric and ratiometric fluorescence probe for copper ions. J. Lumin. 164, 138–145 (2015)

    Article  CAS  Google Scholar 

  47. Yeh, J.T., Chen, W.C., Liu, S.R., Wu, S.P.: A coumarin-based sensitive and selective fluorescent sensor for copper(II) ions. New J. Chem. 38, 4434–4439 (2014)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the financial support of the research council of University of Mazandaran.

Author information

Authors and Affiliations

  1. Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran

    Rahman Hosseinzadeh, Elham Domehri & Mahmood Tajbakhsh

  2. Pharmaceutical Sciences Research Center, Department of Medicinal Chemistry, Mazandaran University of Medical Sciences, Sari, Iran

    Ahmadreza Bekhradnia

Authors
  1. Rahman Hosseinzadeh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Elham Domehri
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mahmood Tajbakhsh
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ahmadreza Bekhradnia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Rahman Hosseinzadeh.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 2767 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hosseinzadeh, R., Domehri, E., Tajbakhsh, M. et al. New fluorescent sensor based on a calix[4]arene bearing two triazole–coumarin units for copper ions: application for Cu2+ detection in human blood serum. J Incl Phenom Macrocycl Chem 93, 245–252 (2019). https://doi.org/10.1007/s10847-018-0872-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-018-0872-3

Keywords

Search

Navigation