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Analytical and Bioanalytical Chemistry

, Volume 402, Issue 10, pp 3253–3260 | Cite as

Fluorescent ion-imprinted polymers for selective Cu(II) optosensing

  • Silvia C. Lopes Pinheiro
  • Ana B. Descalzo
  • Ivo M. RaimundoJr.Email author
  • Guillermo Orellana
  • María C. Moreno-BondiEmail author
Original Paper

Abstract

This paper describes the synthesis and characterization of a fluorescent ion-imprinted polymer (IIP) for selective determination of copper ions in aqueous samples. The IIP has been prepared using a novel functional monomer, 4-[(E)-2-(4′-methyl-2,2′-bipyridin-4-yl)vinyl]phenyl methacrylate (abbreviated as BSOMe) that has been spectroscopically characterized in methanolic solution, in the absence and in the presence of several metal ions, including Cd(II), Cu(II), Hg(II), Ni(II), Pb(II), and Zn(II). The stability constant (2.04 × 108 mol−2 l2) and stoichiometry (L2M) of the BSOMe complex with Cu(II) were extracted thereof. Cu(II)-IIPs were prepared by radical polymerization using stoichiometric amounts of the fluorescent monomer and the template metal ion. The resulting cross-linked network did not show any leaching of the immobilized ligand allowing determination of Cu(II) in aqueous samples by fluorescence quenching measurements. Several parameters affecting optosensor performance have been optimized, including sample pH, ionic strength, or polymer regeneration for online analysis of water samples. The synthesized Cu(II)-IIP exhibits a detection limit of 0.04 μmol l−1 for the determination of Cu(II) in water samples with a reproducibility of 3%, exhibiting an excellent selectivity towards the template ion over other metal ions with the same charge and close ionic radius. The IIP-based optosensor has been repeatedly used and regenerated for more than 50 cycles without a significant decrease in the luminescent properties and binding affinity of the sensing phase.

Keywords

Optical sensors Fluorescence MIP Heavy metals Copper ions 

Notes

Acknowledgments

The authors thank financial support from CAPES (CAPES/DGU 125/06), the Spanish Ministry of Education and Ministry of Science and Innovation (PHB2005-0030-PC, CTQ2009-14565-C03), and Complutense University (GR58-08-910072). FAPESP (05/04258-6) and National Institute of Advanced Analytical Science and Technology-INCTAA (CNPq 573894/2008-6 and FAPESP 2008/57808-1) are also gratefully acknowledged.

Supplementary material

216_2011_5620_MOESM1_ESM.pdf (254 kb)
ESM 1 (PDF 254 kb)

References

  1. 1.
    Sellergren B (ed) (2001) Molecularly imprinted polymers. Man made mimics of antibodies and their applications in analytical chemistry. Elsevier, Amsterdam, The NetherlandsGoogle Scholar
  2. 2.
    Moreno-Bondi MC, Navarro-Villoslada F, Benito-Peña E, Urraca JL (2008) Molecularly imprinted polymers as selective recognition elements in optical sensing. Curr Anal Chem 4:316–340CrossRefGoogle Scholar
  3. 3.
    Chen L, Xuab S, Lia J (2011) Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev 40:2922–2942CrossRefGoogle Scholar
  4. 4.
    Maier NM, Lindner W (2007) Chiral recognition applications of molecularly imprinted polymers: a critical review. Anal Bioanal Chem 389:377–397CrossRefGoogle Scholar
  5. 5.
    Tse Sum Bui T, Haupt K (2010) Molecularly imprinted polymers: synthetic receptors in bioanalysis. Anal Bioanal Chem 398:2481–2492CrossRefGoogle Scholar
  6. 6.
    Suriyanarayana S, Cywinski PJ, Moro AJ, Mohr GJ, Kutner W (2011) Chemosensors based on molecularly imprinted polymers. Top Curr Chem. doi: 10.1007/128_2010_92
  7. 7.
    Moreno Bondi MC, Benito Peña ME, Urraca JL, Orellana G (2011) Immuno-like assays and biomimetic microchips. Top Curr Chem. doi: 10.1007/128_2010_94
  8. 8.
    Prasada Rao T, Kala R, Daniel S (2006) Metal ion-imprinted polymers—novel materials for selective recognition of inorganics. Anal Chim Acta 578:105–116CrossRefGoogle Scholar
  9. 9.
    Özkara S, Andaç M, Karakoç V, Say R, Denizli A (2011) Ion-imprinted PHEMA based monolith for the removal of Fe3+ ions from aqueous solutions. J Appl Polym Sci 120:1829–1836CrossRefGoogle Scholar
  10. 10.
    Shamsipur M, Besharati-Seidani A (2011) Synthesis of a novel nanostructured ion-imprinted polymer for very fast and highly selective recognition of copper(II) ions in aqueous media. React Funct Polym 71:131–139CrossRefGoogle Scholar
  11. 11.
    Walas S, Tobiasz A, Gawin M, Trzewik B, Strojny M, Mrowiec H (2008) Application of a metal ion-imprinted polymer based on salen–Cu complex to flow injection preconcentration and FAAS determination of copper. Talanta 76:96–101CrossRefGoogle Scholar
  12. 12.
    Araki K, Marumaya T, Kamiya N, Goto M (2005) Metal ion-selective membrane prepared by surface molecular imprinting. J Chromatogr B 818:141–145CrossRefGoogle Scholar
  13. 13.
    Taher A, Somaye A (2011) Preparation of nano-sized Pb2+ imprinted polymer and its application as the chemical interface of an electrochemical sensor for toxic lead determination in different real samples. J Hazard Mater 190:451–459CrossRefGoogle Scholar
  14. 14.
    World Health Organization (2004) Copper in drinking-water. Background document for development of WHO guidelines for drinking-water quality. World Health Organization, http://www.who.int/water_sanitation_health/dwq/chemicals/copper.pdf
  15. 15.
    Say R, Birlik E, Eröz A, Yilmaz F, Gedikbey T, Denizli A (2003) Preconcentration of copper on ion-selective imprinted polymer microbeads. Anal Chim Acta 480:251–258CrossRefGoogle Scholar
  16. 16.
    Dakova I, Karadjova I, Ivanov I, Georgieva V, Evtimova B, Georgiev G (2007) Solid phase selective separation and preconcentration of Cu(II) by Cu(II)-imprinted polymethacrylic microbeads. Anal Chim Acta 584:196–203CrossRefGoogle Scholar
  17. 17.
    Shamsipur M, Fasihi J, Khanchi A, Hassani R, Alizadeh K, Shamsipur H (2007) A stoichiometric imprinted chelating resin for selective recognition of copper(II) ions in aqueous media. Anal Chim Acta 599:294–301CrossRefGoogle Scholar
  18. 18.
    Wang S, Zhang R (2006) Selective solid-phase extraction of trace copper ions in aqueous solution with a Cu(II)-imprinted interpenetrating polymer network gel prepared by ionic imprinted polymer (IIP) technique. Microchim Acta 154:73–80CrossRefGoogle Scholar
  19. 19.
    Birlik E, Eröz A, Denizli A, Say R (2006) Preconcentration of copper using double-imprinted polymer via solid phase extraction. Anal Chim Acta 565:145–151CrossRefGoogle Scholar
  20. 20.
    Dam HA, Kim D (2009) Selective copper(II) sorption behavior of surface-imprinted core-shell-type polymethacrylate microspheres. Ind Eng Chem Res 48:5679–5685CrossRefGoogle Scholar
  21. 21.
    Jo SH, Park C, Yi SC, Kim D, Mun S (2011) Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions, cobalt ions, and the constituent metal ions of the buffer solution used as eluent. J Chromatogr A 1218:5664–5674CrossRefGoogle Scholar
  22. 22.
    Rongning L, Ruiming Z, Wenjing S, Xuefeng H, Wei Q (2011) Potentiometric sensor based on an ion-imprinted polymer for determination of copper. Sens Lett 9:557–562CrossRefGoogle Scholar
  23. 23.
    Zheng-Peng Y, Chun-Jing Z (2009) Designing of MIP-based QCM sensor for the determination of Cu(II) ions in solution. Sensors Actuator B 142:210–215CrossRefGoogle Scholar
  24. 24.
    Sing-Muk N, Narayanaswamy R (2010) Demonstration of a simple, economical and practical technique utilising an imprinted polymer for metal ion sensing. Microchim Acta 169:303–311CrossRefGoogle Scholar
  25. 25.
    Pinheiro SCL, Raimundo IM Jr, Moreno-Bondi MC, Orellana G (2010) Simultaneous determination of copper, mercury and zinc in water with a tailored fluorescent bipyridine ligand entrapped in silica sol–gel. Anal Bioanal Chem 398:3127–3138CrossRefGoogle Scholar
  26. 26.
    Likhtenshtein G (2010) Stilbenes. Applications in chemistry, life sciences and materials science. Wiley, New YorkGoogle Scholar
  27. 27.
    Lakowicz JR (2006) Principles of fluorescence spectroscopy, 3rd edn. Springer, New YorkCrossRefGoogle Scholar
  28. 28.
    Orellana G, Urraca JU, Ribeiro dos Santos A “Method for preparing thin films in optical sensors” PCT Patent Appl. WO2011/009981Google Scholar
  29. 29.
    Miller JC, Miller JN (2005) Statistics for analytical chemistry, 5th edn. Pearson Education, EssexGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Silvia C. Lopes Pinheiro
    • 1
    • 2
  • Ana B. Descalzo
    • 2
  • Ivo M. RaimundoJr.
    • 1
    Email author
  • Guillermo Orellana
    • 2
  • María C. Moreno-Bondi
    • 2
    Email author
  1. 1.Institute of ChemistryUniversity of CampinasCampinasBrazil
  2. 2.Optical Chemosensors and Applied Photochemistry Group (GSOLFA), Faculty of ChemistryUniversidad Complutense de MadridMadridSpain

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