ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY VOLUME 2

ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY VOLUME 2

MODERN ANALYTICAL CHEMISTRY Series Editor: David Hercules University of Pittsburgh ANALYTICAL ATOMIC SPECTROSCOPY By William G. Schrenk PHOTOELECTRON AND AUGER SPECTROSCOPY By Thomas A. Carlson MODERN FLUORESCENCE SPECTROSCOPY, VOLUME 1 Edited by E. L. Wehry MODERN FLUORESCENCE SPECTROSCOPY, VOLUME 2 Edited by E. L. Wehry APPLIED ATOMIC SPECTROSCOPY, VOLUME 1 Edited by E. L. Grove APPLIED ATOMIC SPECTROSCOPY, VOLUME 2 Edited by E. L. Grove TRANSFORM TECHNIQUES IN CHEMISTRY Edited by Peter R. Griffiths ION SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY, VOLUME 1 Edited by Henry Freiser ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY, VOLUME 2 Edited by Henry Freiser

ION-SELECTIVE ELECTRODES IN ANALYTICAL CHEMISTRY VOLUME 2 Edited by Henry Freiser University of Arizona Tucson, Arizona PLENUM PRESS NEW YORK AND LONDON

Main entry under title: Library of Congress Cataloging in Publication Data Ion-selective electrodes in analytical chemistry. (Modern analytical chemistry) Includes bibliographical references and index. 1. Electrodes, Ion selective. I. Freiser, Henry, 1920- QD571.159 543'.087 ISBN-13: 978-1-4684-3778-2 e-isbn-13: 978-1-4684-3776-8 DOl: 10.1007/978-1-4684-3776-8 78-16722 1980 Plenum Press, New York Softcover reprint of the hardcover 15t edition 1980 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y. 10011 All righ ts reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

Contributors Richard P. Buck. Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina Henry Freiser. Department of Chemistry, University of Arizona, Tucson, Arizona Robert J. Huber. Department of Electrical Engineering, University of Utah, Salt Lake City, Utah Jifi Janata. Department of Bioengineering, University of Utah, Salt Lake City, Utah Robert K. Kobos. Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia Owen R. Melroy. Graduate Student, Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina James C. Thompsen. Graduate Student, Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina v

Preface We continue in this second volume the plan evident in the first; i.e., of presenting a number of well-rounded up-to-date reviews of important developments in the exciting field of ion-selective electrodes in analytical chemistry. In this volume, in addition to the exciting applications of ISE'S to biochemistry systems represented by the description of enzyme electrodes, there is featured the most recent development in ISE'S, namely, the joining of the electrochemical and solid state expertise, resulting in CHEMFETS. The scholarly survey of the current status of ISE'S will undoubtedly be welcomed by all workers in the field. Tucson, Arizona Henry Freiser vii

Contents Chapter 1 Potentiometric Enzyme Methods Robert K. Kobos 1. Introduction...... 2. Soluble Enzyme Systems... 2.1. Substrate Determinations 2.2. Enzyme Determinations. 2.3. Inhibitor Determinations. 3. Immobilized Enzyme Systems. 3.1. Methods of Immobilization. 3.2. Characteristics of Immobilized Enzymes 3.3. Analytical Applications with Ion-Selective Electrodes 4. Enzyme Electrodes 4.1. Urea Electrodes 4.2. Amygdalin Electrodes 4.3. Glucose Electrodes. 4.4. Penicillin Electrodes 4.5. Amino Acid Electrodes 4.6. Nucleotide Electrodes 4.7. Uric Acid Electrode 4.8. Creatinine Electrode 4.9. Acetylcholine Electrodes. 4.10. D-Gluconate Electrode 4.11. Lactate Electrode 4.12. Inhibitor Determination 4.13. Substrate Electrodes 4.14. Current Trends.... 4.15. Applications of Enzyme Electrodes 4.16. Theoretical Studies... 4.17. Response Characteristics 5. Bacterial Electrodes 5.1. L-Arginine Electrode. 5.2. L-Aspartate Electrode. 5.3. L-Glutamine Electrode ix 1 5 5 13 18 19 19 23 23 31 35 39 40 40 41 46 47 48 48 49 49 50 50 51 56 59 61 69 71 72 73

x Contents 5.4. L-Cysteine Electrode........... 5.5. Nicotinamide Adenine Dinucleotide Electrode 5.6. Nitrate Electrode............. 5.7. Potentiometric-Based Analysis with Bacterial Cells 6. Tissue-Based Electrode......... 7. Future of Potentiometric Enzyme Methods References................ 73 74 75 76 76 77 78 Chapter 2 Coated Wire lon-selective Electrodes Henry Freiser 1. Introduction.... 2. Preparation of Coated Wire Electrodes.. 2.1. Preparation of Electroactive Species 2.2. Polymeric Matrix 2.3. Use of Plasticizers.... 2.4. Construction of the CWE 3. Preconditioning and Storage Procedures 4. Calibration of Coated Wire Electrodes 5. Determination of Selectivity Ratios... 6. Mechanism of CWE Behavior..... 7. Applications of Coated Wire Electrodes 7.1. Anionic Applications of Anionic CWE's 7.2. Analytical Applications of Cationic Electrodes 7.3. Determination of pka and Other Equilibrium Constants 8. Conclusions References........................ 85 86 86 87 88 88 89 90 91 93 101 102 103 104 104 105 Chapter 3 Chemically Sensitive Field Effect Transistors Jifi Janata and Robert J. Huber 1. Introduction 2. Theory of IGFET's........ 2.1. MIS Structure.... 2.2. Current-Voltage Relationships for the IGFET 2.3. CHEMFET............. 3. Practice.... 3.1. CHEMFET Geometry and Encapsulation 3.2. Hydrogen-Ion-Sensitive Feld Effect Transistor 3.3. ISFET's with Solid State Membranes 3.4. ISFET's with Homogeneous Polymeric Membranes 3.5. Heterogeneous Membranes.......... 3.6. Immunochemically Sensitive Field Effect Transistor 3.7. Reference ISFET. 3.8. Measuring Circuitry.............. 107 110 111 116 124 137 l37 142 147 149 153 156 161 167

Contents xi 4. Conclusions Notation... References.. Supplementary References 169 171 172 174 Chapter 4 A Compilation of lon-selective Membrane Electrode Literature Richard P. Buck, James C. Thompsen, and Owen R. Melroy Introduction... 175 Table 1. Highlights in the Development of Membrane Electrodes.. 186 Table 2. Books and Articles on Ion-Selective Electrodes and Closely Related Topics (in Approximately Chronological Order)... 194 Table 3. Reviews of Principles and Applications (in Approximately Chronological Order)... 195 Table 4. Specific Application Reviews for Ion-Selective Electrodes 197 Table 5. Properties and Applications of Fluoride-Selective Electrodes 197 Table 6. Solid State Halide-Sensing Electrodes......... 202 Table 7. Solid State Cyanide Responses............ 206 Table 8. Solid State, Mainly Sulfide-Sensing, Electrodes..... 206 Table 9. Solid State Electrodes for Divalent Ions and Miscellaneous 208 Table 10. Glass Electrodes... 213 Table 11. Liquid Membrane Electrodes-Cation Sensitive 219 Table lla. Liquid Membrane Electrodes-Anion Sensitive 223 Table 12. Neutral-Carrier-Based Electrodes...... 228 Table 13. Gas, Enzyme, and Clinical Electrodes.... 232 Table 14. Classical Synthetic Organic and Inorganic Ion Exchange Membranes... 236 Table 15. Potentiometry and Ion-Selective Electrode Nomenclature. 238 References "A" (1968-1969) 239 "B" (1970-1971) 243 "c" (1972-1973) 253 "D" (1974-1975) 266 "E" (1976-1977) 272 "F" (1978) 280 Index 289