List of Contributors |
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xviii | |
Historical Overview |
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1 | (32) |
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Part 1 Theoretical Background |
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1.1 Elementary Theory of the Interaction of Electromagnetic Fields with Dielectric Materials |
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33 | (27) |
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1.1.1 Electrical Polarization |
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33 | (5) |
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1.1.1.1 Dielectric Polarization in Static Electric Fields |
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33 | (2) |
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1.1.1.2 An Overview of Different Polarization Processes in Atomic and Molecular Dielectrics |
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35 | (1) |
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1.1.1.3 Interactions between Dipoles |
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36 | (2) |
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1.1.2 Dielectric Properties in Time-Dependent Fields |
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38 | (4) |
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1.1.2.1 Complex Dielectric Permittivity and Complex Conductivity |
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38 | (2) |
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1.1.2.2 Relaxation Function |
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40 | (2) |
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1.1.3 Deviations from Debye-Type Behavior |
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42 | (7) |
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1.1.3.1 Phenomenological Dispersion and Relaxation Functions |
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42 | (3) |
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1.1.3.2 Time-Domain Behavior of Dispersion Functions of Havriliak-Negami Type |
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45 | (1) |
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1.1.3.3 Distributions of Relaxation Times as a Means to Relate Time to Frequency Domain |
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45 | (4) |
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1.1.4 Diffusion and Transport in Dielectrics |
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49 | (6) |
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1.1.4.1 Rotational Diffusion |
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49 | (2) |
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1.1.4.2 A Fractal Interpretation of the Non-Debye Behavior |
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51 | (2) |
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1.1.4.3 Percolation Phenomena |
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53 | (2) |
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55 | (5) |
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1.2 Theory of Suspensions of Particles in Homogeneous Fields |
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60 | (24) |
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1.2.1 Maxwell-Wagner Polarization and Relaxation |
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60 | (4) |
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60 | (1) |
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1.2.1.2 Origin of the Interfacial Polarization: Layered Dielectrics |
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61 | (3) |
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1.2.2 Suspensions of Homogeneous Particles Distributed at Random in an Electrolyte |
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64 | (4) |
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1.2.2.1 Spherical Particles |
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64 | (3) |
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1.2.2.2 Suspensions of Ellipsoidal Particles in Homogeneous Electric Fields |
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67 | (1) |
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1.2.3 Inhomogeneous Particles |
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68 | (10) |
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1.2.3.1 The Single-Shell Model of Spherical Particles |
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68 | (3) |
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1.2.3.2 Multi-Shell Models for Spherical Particles |
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71 | (1) |
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1.2.3.3 The Simplified Two-Shell Model |
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72 | (5) |
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1.2.3.4 Model for Shelled Ellipsoidal Particles |
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77 | (1) |
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1.2.4 Concentrated Suspensions |
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78 | (2) |
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1.2.4.1 The Bottcher-Polder-Van Santen Correction for the Far-Field Effect-the Substitution Method |
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78 | (1) |
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1.2.4.2 The Bruggeman-Hanai Correction for the Far-Field Effect-the Integral Method |
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79 | (1) |
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1.2.5 Practical Implementation of Particle Suspension Models |
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80 | (2) |
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1.2.5.1 Implementation of Realistic Cell Models |
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80 | (1) |
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1.2.5.2 Numerical Calculation of Permittivity of Concentrated Suspensions |
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81 | (1) |
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82 | (2) |
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1.3 Dielectric Models and Computer Simulations for Complex Aggregates |
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84 | (25) |
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84 | (1) |
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1.3.2 Modeling Cellular Aggregation by Incorporating Near-Field Corrections |
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85 | (6) |
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1.3.2.1 Dipole-Dipole Interactions in Random Suspensions of Aggregates |
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85 | (1) |
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1.3.2.2 Useful Particular Cases of the Aggregate Model |
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86 | (2) |
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1.3.2.3 Looyenga-Landau-Lifshitz Theory for Percolative Fractal Structures |
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88 | (3) |
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1.3.3 Electrical-Element Method for Modeling Cantorian Fractals |
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91 | (5) |
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1.3.3.1 Theoretical Models for Rough Interfaces and Cantorian Trees |
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91 | (3) |
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1.3.3.2 Computations for Frequency Spectra of Permittivity and Conductivity |
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94 | (2) |
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1.3.4 Numerical Modeling of Cell Aggregates |
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96 | (7) |
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1.3.4.1 Simple Aggregates |
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96 | (3) |
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1.3.4.2 Complex Aggregates |
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99 | (4) |
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103 | (6) |
Part 2 Experimental Methods and Techniques |
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109 | (31) |
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2.1.1 Electromagnetic Waves and Dielectric Spectroscopy |
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109 | (3) |
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2.1.1.1 Sample Cells Much Smaller than the Wavelengths of the Field |
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110 | (1) |
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2.1.1.2 Measurement Probe Size Comparable to the Wavelength of the Field |
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111 | (1) |
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2.1.1.3 Sample Size Much Larger than the Wavelength of the Field |
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112 | (1) |
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2.1.2 Audio- and Radiofrequency Methods |
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112 | (8) |
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2.1.2.1 Automatic RLC Bridges and Impedance Analyzers |
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113 | (1) |
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2.1.2.2 Time-Domain Spectrometers |
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114 | (1) |
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2.1.2.3 Choice of Measurement Cells and Corrections for Spurious Contributions |
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115 | (5) |
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120 | (12) |
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2.1.3.1 Distributed Transmission Line and Resonator Structures |
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120 | (4) |
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2.1.3.2 Broadband Coaxial Line Technology |
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124 | (4) |
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2.1.3.3 Miniaturized Structures |
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128 | (2) |
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2.1.3.4 Spectroscopic Imaging |
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130 | (2) |
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132 | (8) |
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2.2 Electrode Polarization |
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140 | (30) |
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140 | (2) |
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2.2.1.1 Overview of the Physical Phenomena |
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140 | (1) |
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140 | (2) |
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2.2.2 Physical and Electrochemical Models for Electrode Polarization |
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142 | (6) |
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2.2.2.1 The Gouy-Chapman-Stern Model |
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142 | (2) |
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2.2.2.2 Equivalent Circuits with Lumped Elements |
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144 | (2) |
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2.2.2.3 Circuits with Distributed Elements |
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146 | (1) |
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2.2.2.4 Summing up the Discussion |
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147 | (1) |
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2.2.3 Reduction of EP Contributions through Electrode Treatments |
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148 | (5) |
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149 | (1) |
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2.2.3.2 Blocking Electrodes |
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150 | (3) |
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2.2.4 Data Post-Processing Techniques for EP Contribution Correction |
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153 | (7) |
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2.2.4.1 The Substitution Method |
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153 | (1) |
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2.2.4.2 Frequency- and Time-Variation Approaches |
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154 | (1) |
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2.2.4.3 The Frequency-Derivative Method |
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155 | (1) |
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2.2.4.4 Comparison and Substitution Methods |
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156 | (1) |
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2.2.4.5 Methods Based on Data Fitting to Theoretical Models |
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157 | (3) |
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2.2.5 Hardware-Based Techniques |
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160 | (4) |
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2.2.5.1 Electrode Distance Variation Technique |
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160 | (1) |
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2.2.5.2 Four-Electrode Techniques |
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161 | (2) |
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2.2.5.3 Electrode-Less Methods Based on Electromagnetic Induction |
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163 | (1) |
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164 | (1) |
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164 | (6) |
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2.3 Analysis of Experimental Data and Fitting Problems |
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170 | (19) |
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170 | (3) |
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2.3.1.1 Dielectric Dispersion Functions |
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170 | (1) |
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2.3.1.2 Representation of Dielectric Data |
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171 | (2) |
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2.3.2 Modeling Dielectric Processes |
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173 | (8) |
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2.3.2.1 Electrode Polarization in Dielectric Modeling |
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176 | (1) |
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2.3.2.2 Exploiting the Kramers-Kronig Relationships |
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176 | (1) |
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2.3.2.3 Building the Model Function |
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177 | (4) |
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2.3.3 An Example from the Literature |
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181 | (3) |
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184 | (1) |
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184 | (5) |
Part 3 Applications |
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3.1 Dielectric Relaxation of Water |
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189 | (39) |
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3.1.1 Structure and Dielectric Properties of Water |
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189 | (11) |
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3.1.1.1 Architecture of the Water Molecule and Water Structure |
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189 | (3) |
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3.1.1.2 Dielectric Spectrum of Water |
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192 | (4) |
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3.1.1.3 Wait-and-Switch Relaxation Model |
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196 | (3) |
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3.1.1.4 Hydrogen Ions and the pH |
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199 | (1) |
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3.1.2 Microwave Permittivity Spectra of Aqueous Solutions |
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200 | (5) |
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3.1.2.1 Experimental Data |
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200 | (2) |
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202 | (2) |
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3.1.2.3 The Dipole-Matrix Interaction Concept |
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204 | (1) |
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3.1.3 Static Permittivity of Water and Aqueous Systems |
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205 | (6) |
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3.1.3.1 Dipole Orientation Correlation Factor of Water |
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205 | (1) |
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3.1.3.2 Non-Dipolar Solutes: Mixture Relations |
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206 | (1) |
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3.1.3.3 Electrolyte Solutions, Dielectric Saturation, and Kinetic Depolarization |
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207 | (4) |
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3.1.4 Dipolar Relaxation of Water and Simple Aqueous Solutions |
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211 | (9) |
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3.1.4.1 Hydration Water Relaxation Times |
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211 | (5) |
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3.1.4.2 Water as a Glass Former |
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216 | (2) |
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218 | (2) |
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220 | (1) |
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220 | (8) |
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3.2 Amino Acids and Peptides |
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228 | (20) |
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228 | (11) |
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3.2.1.1 Dielectric Properties of Aqueous Solutions of Amino Acids |
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228 | (11) |
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3.2.2 Oligopeptides and Polypeptides |
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239 | (5) |
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244 | (4) |
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3.3 Dielectric Spectroscopy of Hydrated Biomacromolecules |
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248 | (28) |
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248 | (2) |
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3.3.2 Methods for Sample Preparation |
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250 | (1) |
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3.3.2.1 Amorphous and Crystalline States |
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250 | (1) |
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3.3.2.2 Sample Shapes Employed in Measurements |
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250 | (1) |
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3.3.2.3 Hydration Control |
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250 | (1) |
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3.3.3 Effects of Sample Heterogeneity on Powder Measurements |
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251 | (2) |
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3.3.3.1 Interfacial Effects |
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251 | (1) |
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3.3.3.2 Difficulties Caused by Use of an Insulator between Electrodes and Sample |
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252 | (1) |
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3.3.4 Spectral Features and their Assignments |
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253 | (9) |
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254 | (4) |
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3.3.4.2 High-Frequency Observations and Comparison to Solution States |
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258 | (2) |
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3.3.4.3 Comparison between Different Probes |
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260 | (2) |
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3.3.5 Processes Slower or Faster Than the Main Process |
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262 | (3) |
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263 | (1) |
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264 | (1) |
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264 | (1) |
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3.3.6 Glass Transition and Dynamic Transition |
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265 | (4) |
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3.3.6.1 Definition of the Concept and Literature Review Based on Non-Dielectric Data |
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265 | (2) |
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3.3.6.2 Dielectric Investigation of Glass Transition in Protein Powders |
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267 | (2) |
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269 | (1) |
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269 | (7) |
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3.4 Proteins in Solutions and Natural Membranes |
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276 | (31) |
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276 | (1) |
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3.4.2 Proteins in Aqueous Solutions |
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277 | (6) |
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3.4.2.1 Dielectric Properties of Dilute Globular Protein Solutions |
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277 | (3) |
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3.4.2.2 Concentration Dependence |
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280 | (3) |
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3.4.3 Structural Modification and Protein-Ligand Interaction |
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283 | (4) |
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3.4.3.1 Glucose Oxidase Modification |
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283 | (3) |
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3.4.3.2 Hinge-Bending Motion |
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286 | (1) |
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3.4.4 Effects of pH, Temperature, and Denaturant on Protein Dynamics |
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287 | (5) |
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3.4.4.1 pH-Dependent Dimerization |
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287 | (1) |
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3.4.4.2 Thermal Denaturation |
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288 | (2) |
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3.4.4.3 Denaturation by Urea |
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290 | (2) |
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3.4.5 Proteins in Membranes |
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292 | (8) |
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3.4.5.1 Bacteriorhodopsin and Ferroelectric-Like Behavior |
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292 | (4) |
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3.4.5.2 Membrane Proteins in Living Cells |
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296 | (4) |
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300 | (7) |
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3.5 Dielectric Properties of Polyelectrolytes and Lipid Vesicles |
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307 | (33) |
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307 | (5) |
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307 | (3) |
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310 | (2) |
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3.5.2 Dielectric Spectra of Polyelectrolyte Solutions |
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312 | (11) |
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3.5.2.1 Dielectric Response and Counterion Polarization |
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313 | (2) |
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3.5.2.2 The Scaling Model and the Effect of Concentration on the Relaxation Parameters |
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315 | (3) |
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3.5.2.3 The High-Frequency Relaxation of Water |
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318 | (1) |
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3.5.2.4 What Kind of Information May be Obtained from the Analysis of Dielectric Spectra of a Polyelectrolyte Solution? An Example |
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319 | (4) |
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3.5.3 Electrical Conductivity of Polyelectrolyte |
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323 | (1) |
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3.5.4 Dielectric Spectra of Lipid Vesicles in Aqueous Solutions |
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324 | (1) |
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3.5.5 Studying Polyelectrolyte-Liposome Interactions with Dielectric Methods |
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325 | (7) |
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3.5.5.1 Dielectric Properties |
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325 | (2) |
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3.5.5.2 Conductometric Properties |
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327 | (5) |
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3.5.6 Conclusions and Outlook |
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332 | (1) |
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332 | (8) |
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3.6 Radiofrequency Dielectric Properties of Cell Suspensions |
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340 | (23) |
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340 | (2) |
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3.6.1.1 Overview of Dielectric Dispersion of Cell Suspensions |
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341 | (1) |
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3.6.1.2 Organization of the Chapter |
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342 | (1) |
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3.6.2 Modeling of Cells for Analysis of n-Dispersion |
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342 | (4) |
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3.6.2.1 Simple and Composite Cells |
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342 | (2) |
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3.6.2.2 Cell Shape Effects |
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344 | (2) |
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3.6.3 Electrical Properties of Cell Components as Inferred From the p-Dispersion |
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346 | (7) |
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347 | (4) |
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351 | (1) |
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3.6.3.3 Effects of Layers External to the Plasma Membrane |
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351 | (2) |
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3.6.4 Membrane Properties Associated with a-Dispersion |
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353 | (6) |
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354 | (1) |
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355 | (1) |
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3.6.4.3 Membrane Disruption |
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356 | (1) |
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3.6.4.4 Mobile Charges in Membranes |
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357 | (2) |
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359 | (4) |
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3.7 Dielectric Properties of Blood and Blood Components |
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363 | (25) |
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3.7.1 Dielectric Properties of Red Blood Cells |
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363 | (13) |
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3.7.1.1 Effects of Erythrocyte Morphology |
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364 | (5) |
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3.7.1.2 Temporal Changes of Preserved Erythrocytes |
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369 | (4) |
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3.7.1.3 Effect of Glucose |
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373 | (3) |
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3.7.2 Blood Cell Aggregation |
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376 | (5) |
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3.7.2.1 Rouleaux Formation |
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376 | (2) |
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3.7.2.2 Blood Coagulation |
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378 | (3) |
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3.7.3 Dielectric Properties of Other Blood Cells |
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381 | (3) |
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3.7.3.1 Healthy Leukocytes |
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382 | (1) |
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3.7.3.2 Malignant Leukocytes |
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383 | (1) |
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384 | (4) |
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3.8 Glucose Detection from Skin Dielectric Measurements |
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388 | (25) |
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388 | (1) |
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3.8.2 Overview of Diabetes as a Disease |
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389 | (1) |
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3.8.3 Physiological Effects of Glucose Changes |
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390 | (5) |
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390 | (2) |
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3.8.3.2 Morphology of Skin and Distribution of Microvascular Blood |
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392 | (2) |
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3.8.3.3 Temperature and Chronobiology |
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394 | (1) |
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3.8.4 Impact of Various Physiological Parameters on Dielectric Properties |
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395 | (7) |
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3.8.4.1 Changes Caused by Blood Perfusion |
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396 | (4) |
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3.8.4.2 Effect of Temperature Changes |
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400 | (1) |
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3.8.4.3 Humidity as a Perturbing Factor |
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401 | (1) |
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402 | (3) |
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3.8.5.1 Tissue Measurement |
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402 | (3) |
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3.8.6 Roadmap to Future Developments |
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405 | (2) |
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407 | |
Appendices |
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Appendix A: The Kramers-Kronig Relations |
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413 | (1) |
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Appendix B: Dielectric Spectra Broadening as the Signature of Dipole-Matrix Interaction |
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414 | (4) |
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418 | (1) |
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Appendix D: Relaxation Kinetics |
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419 | (4) |
Index |
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423 | |