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Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics

Bakker, E.; Buhlmann, P.; Pretsch, E. Chem. Rev. 1997, 97, 3083-3132

(312 cited publications cited this review by August 2003)

I. Introduction

Over the past 30 years, the application of carrier-based ion-selective electrodes (ISEs) has evolved to a well established routine analytical technique. The College of American Pathologists Comprehensive Chemistry Survey in 1980, for example, showed only 22% of the participating laboratories as making potentiometric Na+ or K+ measurements. Already in 1991, on the other hand, the Chemistry Survey listed 96% of 6041 participating laboratories as using Na+ ISE analyzers and only 4% as using flame atomic emission spectrometry. It was estimated that in the USA about 200 million clinical assays of K+ are made every year with valinomycin-based ISEs. 3 Since several other biologically relevant ions are also monitored with solvent polymeric membrane electrodes, it can be safely stated that yearly well over a billion ISE measurements are performed world-wide in clinical laboratories alone. Moreover, ISEs are also utilized in many other fields including physiology, process control, and environmental analysis. They thus form one of the most important groups of chemical sensors. The analytes for which carrier-based ISEs and their counterparts with optical detection have been developed so far are shown in Table 1 and will be discussed in Part 2 of this review. The key components of both types of sensors are lipophilic complexing agents capable of reversibly binding ions. They are usually called ionophores or ion carriers. The latter name reflects the fact that these compounds also catalyze ion transport across hydrophobic membranes. As it will be shown here, their implementation in ion-selective electrodes or optodes is today straightforward.

Contents

Contents 2

I. Introduction 4

II. Characteristics of Potentiometric and Optical Sensors 9

II. 1. Ion-selective electrodes 9

II. 1. A. Response mechanism 9

II. 1. B. Selectivity 15

II. 1. C. Detection limit 30

II. 1. D. Measuring range 35

II. 1. E. Response time 37

II. 2. Ion-selective optodes 40

II. 2. A. Response mechanism 40

II. 2. B. Selectivity 45

II. 2. C. Detection limits 49

II. 2. D. Measuring range 52

II. 2. E. Response time 53

II. 3. Comparison of optical and potentiometric transduction schemes 54

II. 3. A. Response mechanism 54

II. 3. B. Selectivity 56

II. 3. C. Detection limit 59

II. 3. D. Measuring range 59

II. 3. E. Response time 60

II. 3. F. Lifetime 60

III. Specific Requirements for Ionophores and Membrane Matrices 63

III. 1. Ionophores 63

III. 1. A. General Considerations 63

III. 1. B. Modeling of Ionophores 66

III. 1. C. Exchange Kinetics, Reversibility 69

III. 1. D. Lipophilicity 73

III. 2. Other membrane components 76

III. 2. A. Membrane Solvent (Plasticizer) 76

III. 2. B. Ionic Additives 78

III. 2. C. The Polymer Matrix 82

IV. Conclusions 86

References 88

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