Principles of Chemical Sensors / Edition 1

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Overview

There are so many chemical sensor books on the market that adding one more would seem to be a rather unnecessary exercise. My aim has been to provide material that college or graduate level instructors could use when teaching this subject. The focus is on operating principles, rather than on description of specific sensor or even types of sensors. People who regularly referee sensor manuscripts and research proposals may also find it useful as a reference, for testing one or another dubious proposed sensing scheme. Unfortunately, some strange ideas often get through the review process and become a permanent part of the knowledge database. A "food-for-thought" section has been added at the end of each chapter, which is intended to provoke probing questions about such "schemes." Since this is a never-ending process a "food-for-thought" website has been established as a permanent blog that supplements this book. It can be accessed at: chemistry.gatech.edu/faculty/Janata/

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Editorial Reviews

Booknews
Written for students at graduate and upper undergraduate levels. The book is divided into five sections dealing with the four principal modes of transduction: thermal, mass, electrochemical, and optical, as well as a general introduction common to the four types. Annotation c. Book News, Inc., Portland, OR booknews.com
From the Publisher
From the reviews of the second edition:

“Introduces the main operating principles of chemical sensors … . addressed to students of chemistry, physics, and engineering who want to gain knowledge of the working principles of chemical sensors. … excellent ‘teaching’ book for graduate and master students … . experienced researchers in this field can also find useful information on basic concepts of sensing principles. … provide the reader with basic knowledge of this field. … a good ‘teaching’ book on chemical sensors that could be used in introductory courses on this topic.” (María Cruz Moreno-Bondi, Analytical and Bioanalytical Chemistry, Vol. 399, 2011)

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Product Details

  • ISBN-13: 9780306431838
  • Publisher: Springer-Verlag New York, LLC
  • Publication date: 8/28/1989
  • Series: Modern Analytical Chemistry
  • Edition description: Older Edition
  • Edition number: 1
  • Pages: 336
  • Product dimensions: 6.56 (w) x 9.60 (h) x 0.95 (d)

Table of Contents

1 Introduction to Sensors 1

1.1 Introduction 1

1.2 General Response Curve 3

1.3 Origins of Selectivity 10

Food for Thought #1 10

Irreversible Binding 10

Multiple Binding Sites 11

Symbols 11

Reference 11

2 Selectivity 13

2.1 Introduction 13

2.2 Equilibrium-Based Selectivity 13

2.2.1 Shape Recognition 14

2.2.2 Bioselectivity 17

2.2.2.1 Immunochemical Selectivity 18

2.2.2.2 Nucleotide-Based Selectivity 22

2.2.2.3 Aptamers 23

2.2.3 Imprinted Polymers 24

2.2.3.1 Solubility in Organic Materials 26

2.2.3.2 Solubility in Inorganic Materials 28

2.3 Kinetic Selectivity 30

2.3.1 Enzyme Kinetics 30

2.3.2 Zero-Flux-Boundary Sensors 40

2.4 Mass Transport Selectivity 42

2.5 Design of Selective Layers 43

2.5.1 Preparation of the Substrate 43

2.5.2 Immobilization of Specific Binding Sites 46

Food for Thought #2 47

DNA Selectivity 47

Adsorption and Absorption 48

Gas Immunosensors 48

Linear Solubility Energy Relationship 48

Molecular Imprinting 49

Symbols 49

References 50

3 Thermal Sensors 51

3.1 Introduction 51

3.2 General 51

3.3 Push-Pull Operation 52

3.4 Thermometers 53

3.4.1 Platinum or Platinum-Iridrum Alloy Resistors 53

3.4.2 Thermocouples 54

3.4.3 Thermistors 54

3.5 Equivalent Circuits 55

3.6 Examples of Thermal Chemical Sensors 55

3.6.1 Glucose Thermistor 56

3.6.2 Catalytic Gas Sensors 57

3.6.3 Miniaturized Pellistor 61

Food for Thought #3 61

Enzyme Thermistor 61

Equivalent Circuit for a Thermal Sensor 61

Push-Pull Mode 62

Symbols 62

References 62

4 Mass Sensors 63

4.1 Introduction 63

4.2 Mass Sensors Based on Piezoelectric Materials 67

4.2.1 Thickness-Shear-Mode (TSM) Resonators68

4.2.1.1 QCM in the Gas Phase 71

4.2.1.2 QCM in Aerosols and Suspensions 74

4.2.1.3 QCM in Liquids 76

Modeling with Equivalent Electrical Circuits 79

4.2.2 Surface Acoustic Wave Sensors 86

4.2.3 Plate Mode Oscillators 91

4.3 Nonpiezoelectric Mass Sensors 92

4.3.1 Resonant Cantilevers 93

Food for Thought #4 96

Electrochemical Calibration of QCM 96

Gravitational Effects 96

Enzymatic Mass Sensors 96

Determination of Hydration Numbers 96

Impedance Matching 96

Symbols 97

References 98

5 Electrochemical Sensors 99

5.1 Introduction 99

5.2 General Rules of Electrochemistry 100

5.2.1 Thought Experiment I (Curve A) 101

5.2.2 Thought Experiment II (Curve B) 103

5.3 Nature of Interfaces 104

5.4 Nature of the Current-Voltage Curve 107

5.4.1 Throught Experiment III 108

5.4.2 Charge-Transfer Region 109

5.4.3 Mass Transport Region 111

5.5 Determination of Cell Parameters: Experimental Methods 112

5.5.1 Tafel Plots 112

5.5.2 The Equivalent Electrical Circuit Approach 113

Food for Thought #5 116

Electrochemical Divider 116

Electrochemical Immunosensors 116

Interfaces 116

Mixed Potential 117

Nyquist Plots 117

Voltage and Potential 117

Symbols 117

References 118

6 Potentiometric Sensors 119

6.1 Introduction 119

6.2 Ion Sensors 119

6.2.1 Interfaces in Ion Sensors 119

6.2.1.1 Ion-Selective Interface 120

6.2.1.2 Semipermeable Interface 123

6.2.1.3 Nonselective Interface with Low Ret 124

6.2.1.4 Nonselective Interface with High Ret 129

6.2.2 Components of Potentiometric Cells 131

6.2.2.1 Reference Electrodes 131

First Kind 132

Second Kind 132

Redox Reference Electrode 135

Miniaturization of Reference Electrodes 136

6.2.2.2 Ion-Selective Electrodes 138

6.2.2.2.1 Solid Membrane Electrodes 139

Glass Electrode 139

Fluoride Electrode 143

Other Solid-State Ion-Selective

Electrodes 144

6.2.2.2.2 Liquid Membrane Electrodes 146

6.2.3 Assembled Electrochemical Cell 149

6.2.3.1 Symmetrical Ion-Selective Electrodes 151

6.2.3.2 Asymmetric Membrane Ion Sensors 151

6.2.3.2.1 Coated Wire Electrodes 153

6.2.3.2.2 Field-Effect Transistors 156

pH ISFET 162

ISFETs for Other Ions 165

Multiple Ion ISFETs 166

6.3 Potentiometric Sensors for Neutral Species 168

6.3.1 Potentiometric Enzyme Sensors 168

6.3.2 Severinghaus Electrodes 171

6.3.3 Work Function Sensors 173

6.3.3.1 Kelvin Probe 174

6.3.3.2 Suspended Gate Field-Effect Transistor 175

6.3.3.3 Field-Effect Transistors with Semiconductor Gate 176

6.3.3.3.1 Physics of WF Modulation 177

6.3.3.3.2 Chemical Modulation of WF 181

6.3.3.4 High-Temperature Ionic Sensors 189

Food for Thought #6 194

Adsorption FET 194

Contact Potential 194

Liquid Junction Potential 195

Electrochemical Cell 195

Designed "Nonselectivity" 195

Hydrogel ISFET 195

Kelvin Probe 196

"Perfect" Liquid Junction 196

Nonequilibrium Ion-Selective Electrodes 196

Reference Electrode 196

Single-Electrode Measurement 197

Symbols 197

References 198

7 Amperometric Sensors 201

7.1 General Considerations 201

7.2 Microelectrodes 206

7.3 Oxygen Electrodes 208

7.4 Clark Electrode 210

7.5 Amperometric Selectivity 214

7.5.1 Modified Electrodes 216

7.5.2 Potentiodynamic Sensors 220

7.5.3 Amperometric Biosensors 221

7.5.3.1 Oxygen-Based Enzyme Electrodes 223

7.5.3.2 Oxidation of Hydrogen Peroxide 225

7.5.3.3 Direct Oxidation of Glucose Oxidase 227

7.6 Amperometric Fuel Cells 230

7.7 High Temperature Limiting Current Sensors 232

Food for Thought #7 237

Electrode Placement in Potentiometric and Amperometric Measurement 237

Constant Current 238

Fuel Cell Amperometric Sensors 238

Symbols 238

References 239

8 Conductometric Sensors 241

8.1 Introduction 241

8.1.1 The Origin of Sensor Response 242

8.1.1.1 Contact Resistance 244

8.1.1.1.1 Partially Blocked Contacts 245

8.1.1.1.2 Schottky Contacts 245

8.1.1.2 Bulk Resistance 247

8.1.1.3 Surface Resistance 247

8.2 Chemiresistors 248

8.2.1 Thin Metal Film Sensors 248

8.2.2 Semiconductor Film Sensors 249

8.2.2.1 Inorganic Semiconductor Chemiresistors 250

8.2.2.2 Organic Semiconductor Chemiresistors 255

Organic Field-Effect Transistors (OFETs) 258

8.3 AC Conductometric Sensors 259

8.3.1 Gas Membrane Sensors 259

8.3.2 Dielectrometric Sensors 260

8.3.3 Interfacial Charge Sensors 261

Food for Thought #8 263

Bubbles 263

Closed Circuit 263

Capacitive pH Sensors 263

Channel Conductivity Sensors 263

Immunocapacitor 264

Ion Channel Sensors 264

Polyelectrolyte Sensors 264

Missing Warburg 264

Symbols 265

References 266

9 Optical Sensors 267

9.1 Introduction 267

9.2 Corpuscular Properties of Light 268

9.2.1 The Lambert-Beer Law 270

9.2.2 Luminescence 272

9.3 Wavelike Properties of Light 276

9.3.1 Guiding of Light 278

9.3.2 Coupling of Light 281

9.3.3 Guided Modes 282

9.3.4 Reflectance 284

9.3.4.1 Diffuse Reflectance 284

9.3.4.2 Plasmon Resonance 286

9.3.5 Photoluminescent Schottky Diodes 288

9.4 Selectivity 291

9.4.1 Design of Optical Sensors 292

9.4.2 Optical Arrays 297

9.4.3 Optical Ion Sensors 299

9.4.4 Fluorescence Gas Sensors 303

9.4.5 Optical Biosensors 305

Food for Thought #9 308

Activities 308

Evanescent Field 308

Optrodes in Dilute Solutions 309

Symbols 309

References 310

10 Multivariate Sensing 313

10.1 Introduction 313

10.2 Higher-Order Sensors 314

10.3 Sensing Arrays 317

10.4 Multivariate Analysis 318

10.4.1 Preprocessing of Input Data 318

10.4.2 Data Display 319

10.4.3 Data Processing 319

10.4.3.1 Principal Component Analysis 321

10.4.3.2 Principal Component Regression 322

10.4.3.3 Partial Least Squares 323

10.4.3.4 Self-organizing Maps 324

10.4.3.5 Neural Networks 325

10.4.3.6 Cluster Analysis 327

10.4.3.7 Visual-Empirical Region-of-Influence 328

10.4.3.8 Hybrid Approaches 329

10.4.4 Evaluation Dynamic Data 330

10.4.4.1 Time as a Parameter 330

10.4.4.2 Spatial Information Obtained with Sensing Arrays 332

Food for Thought #10 338

Beauty Contest 338

Artificial Neural Networks 339

Symbols 339

References 339

A Survey of Thermodynamics 341

A.1 Introduction 341

A.2 The First Law 341

A.3 The Second Law 342

A.3.1 The Equilibrium 343

A.3.2 Chemical Potential 344

A.3.3 Ideal: Real Solutions 345

A.3.4 Absorption 345

A.3.5 Adsorption 346

A.3.6 Phase Equilibria 347

B Survey of Kinetics 349

B.1 Equilibrium and Rate Equations 349

B.2 Activation Energy 350

B.3 Diffusion 351

C Survey of Solid-State Physics 353

C.1 Introduction 353

C.2 The Semiconductor Field Effect 359

C.3 Current-Voltage Relationships for the IGFET 360

Reference 365

D Conversions of Equivalent Electrical Circuits 367

Index 369

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