Ion-Selective Electrodes With Ionophore-Doped Sensing Membranes

2576 Supramolecular devices
life time and robustness, reduce the frequency of calibration,
and find new applications for ISEs. However, since
ionophores are the key to the high selectivities of ISEs,
it is clear that the development of new ionophores will
remain an activity central to ion-selective potentiometry.
For a small number of ions the available ionophores are
selective enough for all but very few applications. This
seems to be true, for example, for H + ,Na + ,K + ,Ca 2+ ,and
Ag + . However, this list is short, and many cations are missing
from it. For example, more selective Mg 2+ +
and NH 4
ionophores would be useful for a variety of practical applications.
Moreover, anions are conspicuously absent from
this list. For example, more selective ISEs for the strongly
hydrophilic phosphate and sulfate are still much in need,
and could have a strong impact on clinical, biochemical,
process and environmental analysis. Even for chloride reliable,
more selective sensors for clinical analysis would be
highly desirable. While arrays of sensors with low selectivity
(“electronic tongues” and “electronic noses”) 167 can
serve a purpose when samples contain a limited number
of well-known compounds in a limited range of concentrations,
it has become clear that highly selective sensors are
always preferred for measurements with high accuracy and
precision.
The need for better ionophores will make sure that the
work of those who practice host–guest chemistry will
continue to be much valued in ion-selective potentiometry.
Care must, however, be taken to ensure that reported
selectivities are reproducible and accurately reflect the
thermodynamics of complex stoichiometries and complex
136, 161
stabilities. There is an ever increasing number of
reports on ISEs based on new ionophores, but not all
reported work reflects on the full complexity and potential
of the often hard to synthesize ionophores. It is the hope
of the authors that this chapter has contributed to span the
gap between on one hand (too) simple introductions to ISEs
and, on the other hand, the intimidating plethora of recent
publications written for the specialist.
REFERENCES
1. W. E. Morf, The Principles of Ion-Selective Electrodes and
of Membrane Transport, Elsevier, New York, 1981.
2. D. Ammann, P. Anker, P. C. Meier, et al., Ion Sel. Electrode
R., 1983, 5, 3–92.
3. E. Bakker, P. Bühlmann, and E. Pretsch, Chem. Rev., 1997,
97, 3083–3132.
4. P. Bühlmann, E. Pretsch, and E. Bakker, Chem. Rev., 1998,
98, 1593–1687.
5. E. Lindner and R. P. Buck, Anal. Chem., 2000, 72,
336A–345A.
6. E. Bakker and E. Pretsch, Anal. Chem., 2002, 74,
420A–426A.
7. J. Bobacka, A. Ivaska, and A. Lewenstam, Chem. Rev.,
2008, 108, 329–351.
8. E. Bakker and E. Pretsch, Trends Anal. Chem., 2001, 20,
11–19.
9. T. Sokalski, A. Ceresa, T. Zwickl, and E. Pretsch, J. Am.
Chem. Soc., 1997, 119, 11347.
10. T. Sokalski, A. Ceresa, M. Fibbioli, et al., Anal. Chem.,
1999, 71, 1210–1214.
11. A. Ceresa, E. Bakker, B. Hattendorf, et al., Anal. Chem.,
2001, 73, 343–351.
12. J. Sutter, A. Radu, S. Peper, et al., Anal. Chim. Acta, 2004,
523, 53–59.
13. A. Michalska, J. Dumanska, and K. Maksymiuk, Anal.
Chem., 2003, 75, 4964–4974.
14. W. Qin, T. Zwickl, and E. Pretsch, Anal. Chem., 2000, 72,
3236–3240.
15. A. Malon, T. Vigassy, E. Bakker, and E. Pretsch, J. Am.
Chem. Soc., 2006, 128, 8154–8155.
16. C. Z. Lai, M. A. Fierke, R. C. da Costa, et al., Anal.
Chem., 2010, 82, 7634–7640.
17. E. Bakker, J. Electrochem. Soc., 1996, 143, L83–L85.
18. M. J. Berrocal, R. D. Johnson, I. H. A. Badr, et al., Anal.
Chem., 2002, 74, 3644–3648.
19. M. C. Frost, M. M. Reynolds, and M. E. Meyerhoff, Biomaterials,
2005, 26, 1685–1693.
20. Y. D. Wu and M. E. Meyerhoff, Talanta, 2008, 75,
642–650.
21. A. E. Martell and R. J. Motekaitis, Coord. Chem. Rev.,
1990, 199, 323–361.
22. K. A. Connors, Binding Constants, John Wiley & Sons,
Ltd, New York, 1987.
23. M. Dole, J. Chem. Educ., 1980, 57, 134.
24. W. G. Hines and R. de Levie, J. Chem. Educ., 2010, 87,
1143–1153.
25. C. Moore and B. C. Pressmann, Biochem. Biophys. Res.
Commun., 1964, 15, 562.
26. Z. Stefanac and W. Simon, Chimia, 1966, 20, 436.
27. M. S. Frant, J. Chem. Educ., 1997, 74, 159–166.
28. H.-K. Wipf, L. A. R. Pioda, Z. Stefanac, and W. Simon,
Helv. Chim. Acta, 1968, 51, 377–381.
29. W. Simon, U. Spichiger, D. Freiner, et al. Bull. Eidg.
Techn. Hochschule Zürich, 1991, Nr. 236, 14.
30. P. C. Gunaratna, W. F. Koch, R. C. Paule, et al., Clin.
Chem., 1992, 38, 1459–1465.
31. R. A. Steiner, M. Oehme, D. Ammann, and W. Simon,
Anal. Chem., 1979, 51, 351–351.
32. T. J. Rink, R. Y. Tsien, and A. E. Warner, Nature, 1980,
283, 658–660.
33. D. Ammann Ion-Selective Microelectrodes, Springer-
Verlag, Berlin, 1986.
34. A. Radomska, E. Bodenszac, S. Glab, and R. Koncki,
Talanta, 2004, 64, 603–608.
35. R. W. Cattrall and I. C. Hamilton, Sel. Electrode. Rev.,
1984, 6, 125–172.