Unexpected complexation behaviour of a sol–gel immobilised dye: the development of an optical copper(II) sensor

(Note: The full text of this document is currently only available in the PDF Version )

Nico A. J. M. Sommerdijk, Andrea Poppe, Ceri A. Gibson and John D. Wright


Abstract

The metal-complexing dye Eriochrome Cyanine R (ECR) has been entrapped in sol–gel composites of good optical quality. The immobilisation of ECR had a dramatic effect on the complexation of metal ions. The strong colour change of aqueous ECR solutions, associated with the complexation of aluminium(iii) ions, was not observed with ECR-containing composites. Instead a selectivity for copper(ii) ions was found and a sensing system for these ions was developed. Thickness and pore structure were optimised to enhance sensitivity, lowering the detection limit for copper(ii) ions to 0.1 ppm. The altered complexation behaviour is discussed in terms of effects of entrapment on entropy and enthalpy changes of complexation.


References

  1. B. Dunn and J. I. Zink, J. Mater. Chem., 1991, 1, 903 RSC.
  2. R. Zusman, C. Rottman, M. Ottolenghi and D. Avnir, J. Non-Cryst. Solids, 1990, 122, 107 CrossRef CAS.
  3. A. K. McEvoy, C. McDonagh and B. D. MacCraith, J. Sol–Gel Sci. Technol., 1997, 8, 1121 Search PubMed.
  4. C. Rottman, M. Ottolenghi, R. Zusman, O. Lev, M. Smith, G. Gong, M. L. Kargan and D. Avnir, Mater. Lett., 1992, 13, 293 CrossRef CAS; M. Tsionsky and O. Lev, Analyst, 1993, 118, 557 RSC.
  5. From W. E. Trun, Anal. Chem., 1948, 20, 1117 Search PubMed.
  6. Z. Marcenko, Spectrophotometric Determination of Elements, Halsted Press, Wiley, Chichester, 1976 Search PubMed.
  7. M. Ahmad and R. Narayanaswamy, Anal. Chim. Acta, 1994, 291, 255 CrossRef CAS.
  8. J. F. Quinson and M. Brun, J. Non-Cryst. Solids, 1988, 99, 151 CAS; M. Brun, A. Lallemand, J. F. Quinson and C. Eyraud, Thermochim. Acta, 1977, 21, 59 CrossRef CAS; K. Ishikiriyama, M. Todoki and K. Motomura, J. Colloid Interface Sci., 1995, 171, 92 CrossRef CAS.
  9. These experiments were carried out at pH 4.5 due to the limited solubility of some of the salts at neutral pH.
  10. S. A. Wallington, T. Labayen, A. Poppe, N. A. J. M. Sommerdijk and J. D. Wright, Sensors Actuators B, 1997, 38–39, 48.
  11. For example: ΔG, ΔH and TΔS for an AlIII–EDTA complex at 20 °C have been determined to be –90.7, +52.8 and 143.6 kJ mol–1, respectively (cited in C. S. G. Phillips and R. J. P. Williams, Inorganic Chemistry, Oxford University Press, Oxford, 1966, vol. II, p. 83) Search PubMed.
  12. J. F. Quinson and M. Brun, Characterisation of porous solids, Elsevier, Amsterdam, 1988 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.