Contributors |
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xvii | |
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Chapter 1 Milestones in the Development of Capillary Electromigration Techniques |
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1 | (20) |
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1 | (2) |
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3 | (3) |
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1.2.1 Apparatus and Capillaries |
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3 | (1) |
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3 | (2) |
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1.2.3 Microchip Capillary Electrophoresis |
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5 | (1) |
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1.3 Electrokinetic Chromatography |
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6 | (2) |
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8 | (3) |
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1.4.1 Capillary Gel Electrophoresis |
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8 | (2) |
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1.4.2 Capillary Isoelectric Focusing |
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10 | (1) |
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1.4.3 Affinity Capillary Electrophoresis |
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10 | (1) |
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1.5 Preconcentration in CE |
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11 | (2) |
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13 | (8) |
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17 | (4) |
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Chapter 2 Theoretical Principles of Capillary Electromigration Methods |
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21 | (24) |
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21 | (3) |
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2.2 Theoretical Aspects of CE |
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24 | (11) |
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2.2.1 Electrokinetic Phenomena and Fundamental Aspects of Electrophoretic Transport |
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24 | (4) |
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2.2.2 The Concept of Mobility and Other Separation Aspects |
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28 | (3) |
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2.2.3 The Continuity Equation and Simulation of Electrophoretic Separations |
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31 | (4) |
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2.3 Survey of Selected CE Aspects Explored Through Theoretical Approaches |
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35 | (3) |
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38 | (7) |
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39 | (6) |
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Chapter 3 Column Technology for Capillary Electromigration Methods |
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45 | (24) |
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45 | (1) |
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46 | (9) |
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47 | (3) |
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3.2.2 Polymeric Additives |
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50 | (5) |
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55 | (4) |
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56 | (1) |
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3.3.2 Hydrophilic Coatings |
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56 | (3) |
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59 | (4) |
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59 | (1) |
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3.4.2 Carbon Nanomaterials |
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60 | (3) |
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63 | (6) |
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64 | (5) |
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Chapter 4 Capillary Electrophoresis in Organic Solvents |
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69 | (44) |
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70 | (3) |
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4.2 Acid-Base Reactions in Organic Solvents |
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73 | (7) |
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4.2.1 pKa and pH in Organic Solvents |
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73 | (7) |
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4.3 Electrically Driven Migration |
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80 | (9) |
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4.3.1 Electroosmosis: Flow of Bulk Solvent |
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80 | (2) |
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4.3.2 Ion Migration, Mobility, and Solvent |
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82 | (7) |
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4.4 Peak Broadening: Separation Efficiency, Plate Height, and Plate Number in Different Solvents |
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89 | (14) |
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4.4.1 Extracolumn Effects |
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90 | (1) |
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4.4.2 Longitudinal Diffusion: The Inevitable Source of Peak Broadening |
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91 | (6) |
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4.4.3 Influence of Solvent on Peak Broadening by Other Sources than Diffusion |
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97 | (6) |
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103 | (5) |
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4.5.1 Exploiting pKa Shifts of Neutral Acids to Create BGEs Buffering for Amines in Methanol |
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103 | (2) |
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4.5.2 Using pKa Shifts in Acetonitrile to Achieve Protonation of Very Weak Bases to Enable CZE Analysis of Acrylamide in Real-World Samples |
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105 | (1) |
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4.5.3 Exploiting Heteroconjugation in Acetonitrile to Generate Charged Phenol-Salicylate Associates Amenable for CZE Analysis |
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106 | (1) |
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4.5.4 Improving CZE Separation of Peptides With Ethanol as Solvent for Microchip CZE/Electrospray Mass Spectrometry |
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107 | (1) |
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108 | (5) |
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109 | (4) |
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Chapter 5 Micellar and Microemulsion Electrokinetic Chromatography |
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113 | (30) |
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5.1 Introduction and Terminology |
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113 | (2) |
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5.2 Physicochemical Background |
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115 | (5) |
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115 | (3) |
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5.2.2 Sodium Dodecyl Sulfate |
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118 | (2) |
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120 | (1) |
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5.3 Separation of Neutral Solutes |
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120 | (10) |
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5.3.1 The Pseudophase Model |
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120 | (2) |
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122 | (1) |
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123 | (2) |
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125 | (5) |
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5.4 Separation of Weak Electrolytes |
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130 | (4) |
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5.4.1 Thermodynamic Models |
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130 | (3) |
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5.4.2 Pseudostationary Ion Exchangers |
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133 | (1) |
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5.5 Comparison of MEKC to MEEKC |
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134 | (1) |
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135 | (1) |
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136 | (7) |
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136 | (7) |
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Chapter 6 Capillary Gel and Sieving Electrophoresis |
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143 | (24) |
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143 | (1) |
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144 | (1) |
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145 | (7) |
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145 | (5) |
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150 | (2) |
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6.3.3 CGE in Two-Dimensional Separation of Proteins |
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152 | (1) |
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6.4 Nucleic Acid Analysis |
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152 | (6) |
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154 | (4) |
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6.5 Miniaturization---Lab-on-a-Chip |
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158 | (3) |
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6.5.1 Commercially Available Chip Electrophoresis |
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160 | (1) |
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161 | (6) |
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161 | (1) |
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161 | (6) |
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Chapter 7 Capillary Isoelectric Focusing |
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167 | (22) |
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168 | (1) |
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7.2 Resolving Power of IEF |
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169 | (1) |
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7.3 Capillary Wall Coating |
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170 | (1) |
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7.3.1 Fused-Silica Capillary |
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170 | (1) |
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7.3.2 Coating on the Inner Wall |
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170 | (1) |
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7.4 The Natural pH Gradient |
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171 | (3) |
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7.4.1 The Carrier Ampholyte |
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171 | (1) |
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7.4.2 Nonlinearity of the Natural pH Gradient |
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172 | (1) |
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7.4.3 Electrode Solutions |
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172 | (1) |
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173 | (1) |
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174 | (3) |
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7.5.1 Coalescence of Focusing Double Peaks |
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174 | (1) |
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7.5.2 Drift of the Natural pH Gradient |
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175 | (2) |
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177 | (1) |
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177 | (2) |
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178 | (1) |
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7.6.2 Use of two Ranking pI Markers |
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178 | (1) |
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179 | (5) |
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7.7.1 Detection Principles |
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179 | (3) |
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7.7.2 Static Single-Point Detection |
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182 | (1) |
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7.7.3 Whole-Column Detection |
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183 | (1) |
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184 | (5) |
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185 | (4) |
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Chapter 8 Capillary Isotachophoresis |
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189 | (20) |
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190 | (1) |
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190 | (6) |
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8.2.1 Electrophoretic Mobility of Ions |
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190 | (1) |
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191 | (1) |
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192 | (1) |
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193 | (1) |
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8.2.5 Qualitative and Quantitative Analysis |
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194 | (1) |
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8.2.6 Separation Optimization |
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195 | (1) |
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196 | (2) |
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196 | (1) |
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197 | (1) |
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8.4 Typical Applications of Conventional ITP |
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198 | (3) |
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8.4.1 Separation of Weak Ions Using pH Effect |
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198 | (1) |
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8.4.2 Separation Using the Solvent Effect |
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198 | (1) |
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8.4.3 Separation of Inorganic Ions Using Complex Formation |
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199 | (1) |
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8.4.4 Note on Minor Component Analysis |
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200 | (1) |
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8.5 ITP as a Preconcentration Technique for CE |
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201 | (6) |
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8.5.1 Transient Isotachophoresis |
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202 | (1) |
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8.5.2 Electrokinetic Supercharging |
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203 | (4) |
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207 | (1) |
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207 | (2) |
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208 | (1) |
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Chapter 9 Capillary Electrochromatography |
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209 | (26) |
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9.1 Background of Capillary Electrochromatography |
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209 | (2) |
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211 | (3) |
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9.3 Basic Instrumentation for CEC |
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214 | (2) |
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9.4 Classification of CEC Columns |
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216 | (4) |
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216 | (3) |
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219 | (1) |
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9.4.3 Open-Tubular Columns |
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220 | (1) |
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9.5 Detection Methods in CEC |
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220 | (5) |
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9.5.1 Ultraviolet Detector |
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221 | (1) |
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9.5.2 Laser-Induced Fluorescence |
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221 | (1) |
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9.5.3 Amperometric Detector |
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221 | (1) |
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9.5.4 Chemiluminescence Detector |
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221 | (1) |
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9.5.5 Microflow Evaporative Light-Scattering Detector |
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222 | (1) |
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9.5.6 Condensation Nucleation Light-Scattering Detection |
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222 | (1) |
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222 | (1) |
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223 | (2) |
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225 | (1) |
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226 | (9) |
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226 | (1) |
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226 | (9) |
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Chapter 10 Method Development and Validation of Capillary Electromigration Methods |
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235 | (34) |
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Cari E. Sanger-van de Griend |
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236 | (1) |
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10.2 Analytical Quality by Design and Method Life Cycle Management |
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237 | (2) |
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239 | (18) |
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10.3.1 Method Development Plan |
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239 | (3) |
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10.3.2 Background Electrolyte |
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242 | (5) |
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247 | (3) |
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10.3.4 Sample Introduction |
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250 | (3) |
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253 | (2) |
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10.3.6 Method Optimization |
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255 | (2) |
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257 | (7) |
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260 | (1) |
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260 | (1) |
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260 | (1) |
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261 | (1) |
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261 | (1) |
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261 | (1) |
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10.4.7 Quantitation Limit |
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262 | (1) |
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10.4.8 System Suitability Testing |
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262 | (2) |
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264 | (5) |
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264 | (5) |
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Chapter 11 Instrumental Platforms for Capillary and Microchip Electromigration Separation Techniques |
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269 | (24) |
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270 | (1) |
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11.2 High-Voltage Power Supplies |
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270 | (1) |
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11.3 Sample Injection for Conventional CE |
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271 | (2) |
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271 | (1) |
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272 | (1) |
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273 | (1) |
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11.5 Detectors for Conventional CE |
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273 | (4) |
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274 | (1) |
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11.5.2 Electrochemical Detection |
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275 | (2) |
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11.6 CE Coupled to Flow Injection |
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277 | (1) |
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11.7 Chip-Based Platforms |
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278 | (3) |
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279 | (2) |
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11.8 Sample Introduction Methods for ME |
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281 | (3) |
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281 | (1) |
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281 | (3) |
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11.9 Detection Systems for ME |
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284 | (1) |
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11.10 High-Throughput Analysis |
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285 | (8) |
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287 | (1) |
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287 | (6) |
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Chapter 12 Coupling of Capillary Electromigration Techniques to Mass Spectrometry |
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293 | (20) |
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293 | (1) |
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12.2 Coupling of Electromigration Techniques to Mass Spectrometry |
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294 | (1) |
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12.3 Interfaces for CE-ESI-MS Coupling |
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295 | (4) |
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12.3.1 Sheath Liquid Interfaces |
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295 | (2) |
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12.3.2 Sheathless Interfaces |
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297 | (2) |
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12.4 Methods and Applications in CE-MS |
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299 | (4) |
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12.4.1 Back Ground Electrolytes for CE-MS |
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299 | (1) |
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12.4.2 Capillary Coatings for CE-MS |
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300 | (1) |
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12.4.3 Parameters of Sheath Liquid in CE-MS |
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301 | (1) |
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12.4.4 Important Applications of CE-MS |
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302 | (1) |
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12.5 Combining MS-Interfering CE Electrolytes With Mass Spectrometry |
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303 | (6) |
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12.5.1 Complete Exchange of the Background Electrolyte |
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305 | (1) |
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12.5.2 Compromise Between Separation and Ionization Efficiency |
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305 | (1) |
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12.5.3 Alternative CE-ESI-Interface |
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306 | (1) |
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12.5.4 Alternative Ionization Techniques |
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306 | (1) |
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12.5.5 Two-Dimensional Separation Techniques |
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307 | (2) |
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309 | (4) |
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309 | (4) |
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Chapter 13 Stacking and Multidimensional Techniques for Capillary Electromigration Methods |
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313 | (22) |
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314 | (1) |
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315 | (7) |
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13.2.1 Stacking Based on Field Enhancement/Amplification |
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315 | (2) |
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13.2.2 Transient Isotachophoresis and Transient Pseudo Isotachophoresis |
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317 | (1) |
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13.2.3 Dynamic pH Junction |
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318 | (1) |
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318 | (1) |
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13.2.5 Analyte Focusing by Micelle Collapse |
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319 | (1) |
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13.2.6 Micelle to Solvent Stacking |
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319 | (1) |
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13.2.7 Combination of Different Stacking Techniques |
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320 | (2) |
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13.3 Multidimensional Capillary Electrophoresis |
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322 | (8) |
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13.3.1 Comprehensive Two-Dimensional Capillary Electrophoresis |
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324 | (2) |
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13.3.2 Heart-Cutting Two-Dimensional Capillary Electrophoresis |
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326 | (1) |
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13.3.3 Online Sample Concentration Techniques in Two-Dimensional Capillary Electrophoresis |
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326 | (4) |
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330 | (5) |
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330 | (1) |
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330 | (5) |
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Chapter 14 Capillary Electrophoresis-Mass Spectrometry for Proteomics |
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335 | (18) |
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335 | (4) |
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14.1.1 Strategies in MS-Based Proteomics |
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337 | (2) |
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14.2 Bottom-Up Proteomics by CE-MS |
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339 | (3) |
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14.3 Top-Down Proteomics by CE-MS |
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342 | (3) |
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14.4 CE-MS Operating Conditions for Proteomic Analysis: Critical Issues and Actual Developments |
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345 | (2) |
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347 | (6) |
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348 | (5) |
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Chapter 15 Separation of Small-Mass Ions |
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353 | (20) |
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353 | (1) |
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15.2 Comparison With Ion Chromatography |
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354 | (3) |
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15.2.1 Developmental Overview |
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354 | (1) |
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15.2.2 Separation Selectivity |
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355 | (1) |
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355 | (1) |
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15.2.4 Separation Efficiency |
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356 | (1) |
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356 | (1) |
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15.3 Simultaneous Separation of Anions and Cations |
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357 | (3) |
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360 | (8) |
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15.4.1 Analysis of Metal Ions |
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360 | (1) |
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360 | (5) |
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15.4.3 Pharmaceutical Analysis |
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365 | (1) |
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15.4.4 Agrochemical Analysis |
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365 | (1) |
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15.4.5 Environmental Monitoring |
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365 | (2) |
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15.4.6 Water Quality Analysis |
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367 | (1) |
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15.4.7 Clinical Diagnostic Applications |
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367 | (1) |
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15.4.8 Food Quality Control |
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367 | (1) |
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368 | (5) |
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368 | (5) |
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Chapter 16 Capillary Electrophoresis of Herbal uamonyarates |
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373 | (24) |
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373 | (1) |
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16.2 Overview of Herbal Carbohydrates |
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374 | (11) |
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16.2.1 Mono-, Oligo-, and Polysaccharides |
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374 | (10) |
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16.2.2 Glycoconjugates: Glycoproteins, Glycolipids, and Glycosaminoglycans |
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384 | (1) |
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16.3 Sample Preparation of Carbohydrates From Herbs |
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385 | (2) |
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16.4 Separation and Detection of Herbal Carbohydrates in CE Analysis |
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387 | (3) |
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16.4.1 Complexation With Borate |
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389 | (1) |
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16.4.2 Strongly Alkaline Conditions |
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390 | (1) |
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16.5 Applications of CE in Herbal Carbohydrates Analysis |
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390 | (1) |
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391 | (6) |
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391 | (1) |
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392 | (5) |
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Chapter 17 Electrophoretic Methods for Characterizing Nanoparticles and Evaluating Their Bio-interactions for Their Further Use as Diagnostic, Imaging, or Therapeutic Tools |
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397 | (26) |
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398 | (1) |
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17.2 Fundamentals of Electrokinetic Methods for the Characterization of NPs |
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398 | (10) |
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17.2.1 Relevance of Electrophoresis for the Characterization of NPs in View of Biomedical Applications |
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398 | (1) |
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17.2.2 Electrokinetic Methodologies for Controlling and Optimizing the Synthesis and Functionalization of NPs |
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399 | (4) |
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17.2.3 Evaluating the Behavior of NPs in the Presence of Biologically Relevant Elements |
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403 | (4) |
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17.2.4 Determination of Binding Parameters From Electrophoretic Data |
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407 | (1) |
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17.3 Application of Electromigration Methods to the Analysis of NPs |
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408 | (7) |
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17.3.1 Control and Characterization of NPs Synthesis and Their Physicochemical Properties |
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408 | (4) |
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17.3.2 Nano-Bio Interactions |
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412 | (2) |
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17.3.3 Characterization of NPs as Drug Delivery Systems |
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414 | (1) |
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17.4 Conclusions and Perspectives |
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415 | (8) |
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415 | (8) |
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Chapter 18 Clinical Chemistry Applications of Capillary Electromigration Methods |
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423 | (30) |
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423 | (1) |
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424 | (1) |
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425 | (1) |
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426 | (1) |
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18.5 Immunology and Immunoassays |
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427 | (3) |
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430 | (2) |
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18.7 Therapeutic Drug Monitoring |
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432 | (3) |
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435 | (3) |
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438 | (2) |
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440 | (2) |
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442 | (11) |
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442 | (1) |
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442 | (11) |
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Chapter 19 Biopharmaceutical Applications of Capillary Electromigration Methods |
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453 | (28) |
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19.1 Introduction: Biopharmaceutical Products Analysis |
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454 | (1) |
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19.2 Capillary Gel Electrophoresis |
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455 | (5) |
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19.2.1 Method Description |
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455 | (1) |
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19.2.2 Example of a Practical Protocol |
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456 | (1) |
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457 | (3) |
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19.3 Capillary Isoelectric Electrophoretic Focusing |
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460 | (4) |
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19.3.1 Method Description |
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460 | (1) |
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19.3.2 Example of Practical Protocols |
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461 | (2) |
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463 | (1) |
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19.4 Capillary Electrophoresis |
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464 | (4) |
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19.4.1 Method Description |
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464 | (1) |
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19.4.2 Example of Practical Protocol |
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465 | (1) |
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466 | (2) |
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19.5 CE Hyphenated With Mass Spectrometry |
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468 | (6) |
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19.5.1 Method Description |
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468 | (1) |
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19.5.2 Example of Practical Protocol |
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469 | (1) |
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470 | (4) |
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474 | (7) |
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474 | (7) |
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Chapter 20 Neuroscience Applications of Capillary Electrophoretic Methods |
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481 | (30) |
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481 | (5) |
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20.1.1 Microdialysis and Other Sampling Strategies in CE |
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482 | (1) |
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20.1.2 CE-Based Metabolomics |
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483 | (1) |
|
20.1.3 Single-Cell Analysis by CE |
|
|
484 | (1) |
|
20.1.4 Role of D-Enantiomers in Neurotransmission |
|
|
485 | (1) |
|
20.2 Applications of CE to Neuroscience |
|
|
486 | (17) |
|
|
494 | (1) |
|
|
495 | (1) |
|
|
496 | (1) |
|
|
497 | (2) |
|
|
499 | (1) |
|
|
499 | (1) |
|
20.2.7 Miscellaneous Applications |
|
|
500 | (3) |
|
20.3 Conclusions and Future Trends |
|
|
503 | (8) |
|
|
504 | (1) |
|
|
504 | (7) |
|
Chapter 21 Food Safety Applications of Capillary Electromigration Methods |
|
|
511 | (36) |
|
|
|
|
|
|
511 | (1) |
|
|
512 | (8) |
|
|
520 | (5) |
|
|
525 | (4) |
|
21.5 Other Contaminants and Pollutants |
|
|
529 | (3) |
|
|
532 | (2) |
|
|
534 | (13) |
|
|
534 | (1) |
|
|
534 | (13) |
|
Chapter 22 Application of Capillary Electromigration Methods for Physicochemical Measurements |
|
|
547 | (46) |
|
|
|
|
548 | (1) |
|
22.2 Determination of Acidity Constants, Ionic Mobilities, and Stokes Radii by CE |
|
|
549 | (8) |
|
22.2.1 Nonlinear Regression Analysis of pH Dependence of Effective Mobility |
|
|
549 | (7) |
|
22.2.2 Internal Standard-Based Method |
|
|
556 | (1) |
|
22.3 Determination of Effective Charges |
|
|
557 | (3) |
|
22.3.1 Calculation from pKa Values |
|
|
557 | (1) |
|
22.3.2 Determination by CE |
|
|
557 | (2) |
|
22.3.3 Determination by CITP |
|
|
559 | (1) |
|
22.4 Determination of Relative Molecular Masses of Proteins by CGE |
|
|
560 | (1) |
|
22.5 Determination of the Isoelectric Points of Proteins and Peptides by CIEF and CE |
|
|
561 | (1) |
|
22.6 Semiempirical Relations Between Electrophoretic Mobility of Peptides and Proteins and Their Charge/Size Ratio |
|
|
562 | (2) |
|
22.7 Determination of Binding Constants of Complexes by CE Methods |
|
|
564 | (7) |
|
22.7.1 Mobility Shift ACE |
|
|
564 | (3) |
|
22.7.2 Multiple-Injection ACE |
|
|
567 | (1) |
|
22.7.3 Partial Filling ACE |
|
|
568 | (1) |
|
22.7.4 Preequilibrated CE |
|
|
569 | (1) |
|
22.7.5 Hummel-Dreyer and Vacancy Peak Methods |
|
|
569 | (1) |
|
22.7.6 Frontal Analysis and Continuous Frontal Analysis CE |
|
|
569 | (1) |
|
22.7.7 Kinetic Capillary Electrophoresis |
|
|
570 | (1) |
|
22.8 Determination of Partition Constants by MEKC and MEEKC |
|
|
571 | (3) |
|
22.9 Determination of Diffusion Coefficients |
|
|
574 | (2) |
|
22.10 Determination of Rate Constants for Chemical and Enzymatic Reactions |
|
|
576 | (6) |
|
|
582 | (11) |
|
|
582 | (1) |
|
|
582 | (11) |
Index |
|
593 | |