Buhlmann, P.; Pretsch, E.; Bakker, E. Chem. Rev. 1998, 98, 1593-1687
(368 publications cited this review by August 2003)
I. Introduction
The first ion-selective electrodes (ISEs) based on bulk membranes containing an ion carrier were introduced more than thirty years ago. It has been estimated that already by 1990 more than 7000 papers on ISEs had been published. ISEs form today one of the most important groups of chemical sensors. On the other hand, bulk membrane optodes have been known for only about ten years. However, a fairly large number of such optodes have been developed in short time because ionophores originally developed for ISEs can often be used without further modification and because the two types of sensors rely on very similar chemical equilibria.
The first of this pair of reviews2 gave a theoretical description of the two sensor types, discussing their response mechanisms, selectivities, detection limits, measuring ranges, response times, and life times. The simultaneous treatment emphasized similarities and differences in the theory of ISEs and optodes and was followed by a general discussion of the requirements on the polymer matrix, membrane solvent, ionic additive, and the carrier. Table 1 of the first of this pair of reviews gave a brief list of the analytes for which carrier-based ISEs and bulk optodes have been developed.
This review describes individual carrier-based ISEs and bulk optodes, ordered according to the analyte for which they have been developed. Many reviews on ISEs have been written, selected topics have been covered in the journal Ion-Selective Electrode Reviews, and a little known electronic database summarizes a large number of data on potentiometric sensors (for a first-time user some knowledge of Japanese seems necessary for utilizing this database). A more readily accessible data collection in book form tabulated selectivity data, detection limits, linear ranges, response slopes and life times of many solid and liquid membrane ISEs up to 1988. However, for many analytes, especially for anions and heavy metal ions, more new carrier-based ISEs have been reported in the last ten years than before. For other ions, as for example for several clinically relevant blood electrolytes, major improvements in sensor performance were achieved in the 1990s and several new classes of ionophores, such as the cup-shaped calixarenes, were introduced only fairly recently. Therefore, it is not surprising that among the roughly 120 most representative ISEs and optodes whose principal properties have been summarized in Appendix I almost two thirds have been described in reports published after 1990. This review is intended to document these new developments of carrier-based ISEs, presenting them together with those in the much younger field of the bulk membrane optodes, and tries to put them in a historical perspective. While other articles have reviewed optodes, this is probably the so far most complete review of bulk membrane optodes. This review is intended to be comprehensive enough to mention all analytes for which carrier-based ISEs or bulk membrane optodes have been developed and is supposed to refer to all classes of ionophores that were reported so far for use in bulk membrane ISEs and optodes. It should provide not only a wide overview of relevant work in the field but should also make it possible for the interested reader to quickly find references to specific sensors. For this purpose we have consulted a large number of original publications, reviews and books, searched the literature published between 1981 and November 1996 using the Science Citation Index, and verified many of the references in the original publications found by these means.
Contents
II. Inorganic Cationic Analytes 9
II. 1. H+-Sensors 9 II. 2. Li+-Sensors 18
II. 3. Na+-Sensors 26
II. 4. K+-Sensors 38
II. 5. Rb+-Sensors 48
II. 6. Cs+-Sensors 49
II. 7. NH4+-Sensors 50
II. 8. Be2+-Sensors 52
II. 9. Mg2+-Sensors 53
II. 10. Ca2+-Sensors 61
II. 11. Sr2+-Sensors 70
II. 12. Ba2+-Sensors 71
II. 13. Mo(VI)-Sensors 75
II. 14. Fe(III)-Sensors 75
II. 15. Cu2+-Sensors 75
II. 16. Ag+-Sensors 78
II. 17. Zn2+-Sensors 84
II. 18. Cd2+-Sensors 86
II. 19. Hg2+-Sensors 87
II. 20. Tl+-Sensors 89
II. 21. Bi3+-Sensors 91
II. 22. Pb2+/PbA+-Sensors 91
II. 23. U(VI)-Sensors 96
II. 24. Sm(III)-Sensors 99
III. Inorganic Anionic Analytes 100
III. 1. CO32- and HCO3- Sensors 100 III. 2. SCN- Sensors 103
III. 3. NO2- Sensors 105
III. 4. NO3- Sensors 110
III. 5. OH- Sensors 111
III. 6. Phosphate Sensors 112
III. 7. Sulfide Sensors 114
III. 8. Sulfite Sensors 115
III. 9. Sulfate Sensors 116
III. 10. Cl- Sensors 117
III. 11. ClO4- Sensors 122
III. 12. SeO32- Sensors 123
III. 13. I- and I3- Sensors 123
III. 14. Sensors for Metal Cyano Complexes 126
IV. Organic Ionic Analytes 127
IV. 1. Sensors for Organic Ammonium Ions 127 IV. 2. Sensors for Guanidinium, Guanidinium Derivatives and Creatinine 133
IV. 3. Sensors for Carboxylates 135
IV. 4. A Sensor for 2-Hydroxybenzhydroxamate 140
IV. 5. Sensors for Nucleotides 141
IV. 6. Sensors for Ionic Surfactants 143
IV. 7. Sensors for Polyionic Analytes such as Heparin and Protamine 145
V. Neutral Analytes 147
V. 1. CO2 Sensors 147 V. 2. Sensors for Ammonia and Organic Amines 148
V. 3. Sensors for Humidity and Water 150
V. 4. SO2 Sensors 151
V. 5. Sensors for Alcohols and Non-Ionic Surfactants 152
V. 6. Sensors for O2 154
VI. Conclusions 156
VII. Acknowledgments 159
VIII. References 160
Appendix I: Properties of a Selection of Representative ISEs and Bulk Optodes 213
Appendix II: Abbreviations 229