Ion-Selective Microelectrodes
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1 Daniel Ammann Ion-Selective Microelectrodes Principles, Design and Application With 153 Figures and 42 Tables Springer-Verlag Berlin Heidelberg New York Tokyo
2 Table of Contents 1 Introduction 1 2 Classification of Ion-Selective Electrodes Types of Membranes Electrode Arrangements Concluding Remarks 7 3 Natural and Synthetic Neutral Carriers for Membrane Electrodes Carriers asaclassof Ionophores Molecular Aspects of the lon-selectivity of Neutral Carriers General Remarks Models for the Design of Neutral Carriers Corey-Pauling-Koltun(CPK) Models Electrostatic Models Quantum Chemical Model Calculations Selectivity-Determining Parameters General Remarks Binding Sites Coordination Number and Cavity Arrangement of the Binding Sites Size of the Carrier Properties of Neutral Carriers for Analytically Relevant Membrane Electrodes Permselectivity Ion- and Ligand-Exchange Kinetics Lipophilicity Highly Cation-Selective Neutral Carriers for Liquid Membrane Electrodes Synthesisof Cation-Selective Neutral Carriers Carriers for Anions Concluding Remarks 40
3 XII Table of Contents 4 Liquid Membrane Electrodes Based on Neutral Carriers Parameters Determining Basic Properties of Solvent Polymerie Membranes Membrane Composition Membrane Solvent Membrane Matrix Membrane Additives Ion-Selective Membrane Solutions for Microelectrodes Composition of Membrane Solutions Solvents for Membrane Solutions Additives for Membrane Solutions Concluding Remarks 61 5 Potentiometrie Measurements of Ion Activities with Neutral Carrier-Based Electrodes Cell Assemblies The Membrane Potential The Nernst and the Nicolsky-Eisenman Equations Electrode Function and Detection Limit Selectivity Factors Activity Coefficients. The Debye-Hückel Formalism Liquid-Junction Potentials. The Henderson Formalism StabilityandReproducibilityofEMF Response Time Lifetime Anion Interference Concluding Remarks 95 6 Construction of Liquid Membrane Microelectrodes GlassTubings Micropipettes Single- Versus Double- or Multi-Barrelled Microelectrodes Electrode Bevelling Tip Observation Silanization Electrode Filling Electrode Shielding Reference Microelectrodes Concluding Remarks 117
4 Table of Contents XIII 7 Use of Neutral Carrier-Based Liquid Membrane Microelectrodes Conceptsof Use Electrode Testing Calibration and Evaluation Impalement Criteria CellDamage Cell Contamination Tip Potentials and Electrical Shunts Limitations Due to Selectivity Concluding Remarks General Aspects of Intracellular Measurements of Ions The Intracellular Space as the Measuring Sample Ion Activity, Concentration of Free Ions, Total Concentration In vitro and in vivo Measurements Organelles, Single Cells, Cell Population Cell Compartmentation Method Specific Properties of Intracellular Measurements of Ions Concluding Remarks Neutral Carrier-Based Liquid Membrane Microelectrodes Intracellular Measurements ofh Distribution ofweakacids and Weak Bases Optical Techniques P Nuclear Magnetic Resonance Spectroscopy Potentiometry SurveyofH + -Selective Microelectrodes Available Liquid Membrane Microelectrodes Microelectrodes Based on 3-Hydroxy-N-octylpicolinamide Microelectrodes Based on the Na + Salt of the Antibiotic Nigericin Microelectrodes Based on p-octadecyloxy-m-chlorophenyl-hydrazone-mesoxalonitrile Microelectrodes Based on Tri-n-dodecylamine ComparisonoftheDifferentMethods Concluding Remarks Intracellular Measurements of Li Intracellular Measurements of Na Techniques Used in Studies of Intracellular Na + 222
5 XIV Table of Contents Surveyof Na + -Selective Microelectrodes Available Liquid Membrane Microelectrodes Microelectrodes Based on Potassium Tetrakis (p-chlorophenyl) borate Microelectrodes Based on the Antibiotic Monensin Microelectrodes Based on the Neutral Carrier ETH Microelectrodes Based on the Neutral Carrier ETH Concluding Remarks Intracellular Measurements of K Surveyof K + -Selective Microelectrodes Comparison of Properties of Classical lon-exchanger and Neutral Carrier-Based Microelectrodes Concluding Remarks Intracellular Measurements of Mg Mg 2 + Null Point for Permeabilized Cell Membranes Metallochromic Indicators P Nuclear Magnetic Resonance Spectroscopy Potentiometry Mg 2+ -SelectiveCarriers Microelectrodes Based on the Neutral Carrier ETH Comparison of the Different Methods Concluding Remarks Intracellular Measurements of Ca Photoproteins Originof Bioluminescence Availability of Photoproteins Properties and Useof Photoproteins Measurement of the Luminescence of Photoproteins Metallochromic Indicators Currently Used Indicators Properties of the Indicators Measurements with Metallochromic Indicators Potentiometry Surveyof Ca 2+ -Selective Microelectrodes Course of the Development of Optimized Neutral Carrier-Based Ca 2 + Microelectrodes Properties of Currently Used Microelectrodes Based on the Neutral Carrier ETH Calibration of Ca 2+ -Selective Microelectrodes for Intracellular Studies 275
6 Table of Contents XV Comparison of the Different Methods Concluding Remarks Other Microelectrodes Impact of Neutral Carrier Microelectrodes Applications of Neutral Carrier-Based Microelectrodes Animal Experimentation Neurosciences. The Mind-Body Problem References Subject Index 339
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