PREFACE xvii ACKNOWLEDGMENTS xix CONTRIBUTORS xxi 1 Critical Evaluation of the Use of Surfactants in Capillary Electrophoresis 1 Jessica L. Felhofer, Karin Y. Chumbimuni-Torres, Maria F. Mora, Gabrielle G. Haby, and Carlos D. Garcý´a 1.1 Introduction 1 1.2 Surfactants for Wall Coatings 4 1.

2.1 Controlling the Electroosmotic Flow 4 1.2.2 Preventing Adsorption to the Capillary 5 1.3 Surfactants as Buffer Additives 6 1.3.1 Micellar Electrokinetic Chromatography 6 1.3.

2 Microemulsion Electrokinetic Chromatography 8 1.3.3 Nonaqueous Capillary Electrophoresis with Added Surfactants 9 1.4 Surfactants for Analyte Preconcentration 9 1.4.1 Sweeping 10 1.4.2 Transient Trapping 11 1.

4.3 Analyte Focusing by Micelle Collapse 12 1.4.4 Micelle to Solvent Stacking 12 1.4.5 Combinations of Preconcentration Methods 12 1.4.6 Cloud Point Extraction 12 1.

5 Surfactants and Detection in CE 14 1.5.1 Mass Spectrometry 14 1.5.2 Electrochemical Detection 15 1.6 Conclusions 16 References 17 2 Sample Stacking: A Versatile Approach for Analyte Enrichment in CE and Microchip-CE 23 Bruno Perlatti, Emanuel Carrilho, and Fernando Armani Aguiar 2.1 Introduction 23 2.2 Isotachophoresis 24 2.

3 Chromatography-Based Sample Stacking 25 2.4 Methods Based on Electrophoretic Mobility and Velocity Manipulation (Electrophoretic Methods) 26 2.4.1 Field-Enhanced Sample Stacking (FESS) 27 2.4.2 Field-Enhanced Sample Injection (FESI) 27 2.4.3 Large-Volume Sample Stacking (LVSS) 28 2.

4.4 Dynamic pH Junction 28 2.5 Sample Stacking in Pseudo-Stationary Phases 29 2.5.1 Field-Enhanced Sample Stacking 29 2.5.2 Hydrodynamic Injection Techniques 30 2.5.

2.1 Normal Stacking Mode (NSM) 30 2.5.2.2 Reverse Electrode Polarity Stacking Mode (REPSM) 30 2.5.2.3 Stacking with Reverse Migrating Micelles (SRMM) 30 2.

5.2.4 Stacking Using Reverse Migrating Micelles and a Water Plug (SRW) 31 2.5.2.5 High-Conductivity Sample Stacking (HCSS) 31 2.5.3 Electrokinetic Injection Techniques 32 2.

5.3.1 Field-Enhanced Sample Injection (FESI-MEKC) 32 2.5.3.2 Field-Enhanced Sample Injection with Reverse Migrating Micelles (FESI-RMM) 32 2.5.4 Sweeping 32 2.

5.5 Combined Techniques 33 2.5.5.1 Dynamic pH Junction: Sweeping 33 2.5.5.2 Selective Exhaustive Injection (SEI) 33 2.

5.6 New Techniques 33 2.6 Stacking Techniques in Microchips 33 2.7 Concluding Remarks 36 References 37 3 Sampling and Quantitative Analysis in Capillary Electrophoresis 41 Petr Kuba´9n, Andrus Seiman, and Mihkel Kaljurand 3.1 Introduction 41 3.2 Injection Techniques in CE 42 3.2.1 Hydrodynamic Sample Injection 43 3.

2.1.1 Principle 43 3.2.1.2 Advantages and Performance 44 3.2.1.

3 Disadvantages 44 3.2.2 Electrokinetic Sample Injection 44 3.2.2.1 Principle 44 3.2.2.

2 Advantages and Performance 45 3.2.2.3 Disadvantages 45 3.2.3 Bias-Free Electrokinetic Injection 45 3.2.4 Extraneous Sample Introduction Accompanying Injections in CE 46 3.

2.5 Sample Stacking 48 3.2.5.1 Principle 48 3.2.5.2 Advantages and Performance 49 3.

2.5.3 Disadvantages 50 3.2.6 Alternative Batch Sample Injection Techniques 50 3.2.6.1 Rotary-Type Injectors for CE 50 3.

2.6.2 Hydrodynamic Sample Splitting as Injection Method for CE 51 3.2.6.3 Electrokinetic Sample Splitting as Injection Method for CE 52 3.2.6.

4 Dual-Opposite End Injection in CE 52 3.3 Micromachined/Microchip Injection Devices 53 3.3.1 Droplet Sampler Based on Digital Microfluidics 53 3.3.2 Wire Loop Injection 54 3.4 Automated Flow Sample Injection and Hyphenated Systems 55 3.4.

1 Introduction 55 3.4.2 Advantages and Performance 56 3.4.3 Disadvantages 57 3.5 Computerized Sampling and Data Analysis 57 3.6 Sampling in Portable CE Instrumentation 58 3.7 Quantitative Analysis in CE 59 3.

7.1 Introduction 59 3.7.2 Quantitative Analysis with HD Injection 59 3.7.3 Quantitative Analysis with EK Injection 60 3.7.4 Validation of the Developed CE Methods 61 3.

7.5 Computer Data Treatment in Quantitative Analysis 61 3.8 Conclusions 62 References 62 4 Practical Considerations for the Design and Implementation of High-Voltage Power Supplies for Capillary and Microchip Capillary Electrophoresis 67 Lucas Blanes, Wendell Karlos Tomazelli Coltro, Renata Mayumi Saito, Claudimir Lucio do Lago, Claude Roux, and Philip Doble 4.1 Introduction 67 4.1.1 High-Voltage Fundamentals 67 4.1.2 Electroosmotic Flow Control 68 4.

1.3 Technical Aspects 70 4.1.4 Construction of Bipolar HVPS from Unipolar HVPS 70 4.1.5 Safety Considerations 71 4.1.6 HVPS Commercially Available 71 4.

1.7 Practical Considerations 72 4.1.8 Alternative Sources of HV 72 4.1.9 HVPS Controllers for MCE 72 4.2 High-Voltage Measurement 73 4.3 Concluding Remarks 74 References 74 5 Artificial Neural Networks in Capillary Electrophoresis 77 Josef Havel, Eladia Marýa Pe~na-Mendez, and Alberto Rojas-Hernandez 5.

1 Introduction 77 5.2 Optimization in CE: From Single Variable Approach Toward Artificial Neural Networks 77 5.2.1 Limitations of "Traditional" Single Variable Approach 79 5.2.2 Multivariate Approach with Experimental Design and Response Surface Modeling 79 5.2.2.

1 Experimental Design 79 5.2.2.2 Response Surface Modeling 80 5.3 Artificial Neural Networks in Electromigration Methods 81 5.3.1 Introduction--Basic Principles of ANN 81 5.3.

2 Optimization Using a Combination of ED and ANN 82 5.3.2.1 Testing of ED-ANN Algorithm 83 5.3.2.2 Practical Applications of ED-ANN 83 5.3.

3 Quantitative CE Analysis and Determination from Overlapped Peaks 84 5.3.3.1 Evaluation of Calibration Plots in CE Using ANN to Increase Precision of Analysis 84 5.3.3.2 ANN in Quantitative CE Analysis from Overlapped Peaks 86 5.3.

4 ANN in CEC and MEKC 86 5.3.5 ANN for Peptides Modeling 88 5.3.6 Classification and Fingerprinting 88 5.3.7 Other Applications 90 5.4 Conclusions 90 Acknowledgments 91 References 91 6 Improving the Separation in Microchip Electrophoresis by Surface Modification 95 M.

Teresa Fernandez-Abedul, Isabel Alvarez-Martos, Francisco Javier Garcýa Alonso, and Agustýn Costa-Garcýa 6.1 Introduction 95 6.2 Strategies for Improving Separation 96 6.2.1 Selection of an Adequate Technique: ME 96 6.2.2 Microchannel Design 96 6.2.

3 Selection of an Appropriate ME Material 96 6.2.4 Optimization of the Working Conditions 97 6.2.5 Surface Modification 97 6.2.5.1 Surface Micro- and Nanostructuring 98 6.

2.5.2 Employment of Energy Sources 99 6.2.5.3 Chemical Surface Modification 99 6.3 Chemical Modifiers 102 6.3.

1 Surfactants 104 6.3.2 Ionic Liquids 105 6.3.3 Nanoparticles 108 6.3.4 Polymers 110 6.4 Conclusions 119 Acknowledgments 120 References 120 7 Capillary Electrophoretic Reactor and Microchip Capillary Electrophoretic Reactor: Dissociation Kinetic Analysis Method for "Complexes" Using Capillary Electrophoretic Separation Process 127 Toru Takahashi and Nobuhiko Iki 7.

1 Introduction 127 7.2 Basic Concept of CER 128 7.3 Dissociation Kinetic Analysis of Metal Complexes Using a CER 129 7.3.1 Determination of the Rate Constants of Dissociation of 1:2 Complexes of Al3þ and Ga3þ with an Azo Dye Ligand 2,20-Dihydroxyazobenzene-5,50-Disulfonate in a CER 130 7.4 Expanding the Scope of the CER to Measurements of Fast Dissociation Kinetics with a Half-Life from Seconds to Dozens of Seconds: Dissociation Kinetic Analysis of Metal Complexes Using a Microchip Capillary Electrophoretic Reactor (mCER) 133 7.5 Expanding the Scope of the CER to the Measurement of Slow Dissociation Kinetics with a Half-Life of Hours 135 7.5.

1 Principle of LS-CER 135 7.5.2 Application of LS-CER to the Ti(IV)-Catechin Complex 136 7.5.3 Application of LS-CER to the Ti(IV)-Tiron Complex 138 7.6 Expanding the Scope of CER to Measurement of the Dissociation Kinetics of Biomolecular Complexes 139 7.6.1 Dissociation Kinetic Analysis of [SSB-ssDNA] Using CER 139 7.

7 Conclusions 142 References 142 8 Capacitively Coupled Contactless Conductivity Detection (C4D) Applied to Capillary Electrophoresis (CE) and Microchip Electrophoresis (MCE) 145 Jose Alberto Fracassi da Silva, Claudimir Lucio do Lago, Dosil Pereira de Jesus, and Wendell Karlos Tomazelli Coltro 8.1 Introduction 145 8.2 Theory of C4D 145 8.2.1 Basic Principles of C4D 145 8.2.2 Simulation 146 8.2.

3 Basic Equation for Sensitivity 147 8.2.4 Equivalent Circuit of a CE-C4D System 147 8.2.5 Practical Guidelines 148 8.3 C4D Applied to Capillary Electrophoresis 148 8.3.1 Instrumental Aspects in CE 149 8.

3.2 Coupling C4D with UV-Vis Photometric Detectors in CE 149 8.3.3 Fundamental Studies in Capillary Electrophoresis Using C4D 149 8.3.4 Fundamental Studies on C4D 149 8.3.5 Applications 150 8.

4 C4D Applied to Microchip Capillary Electrophoresis 151 8.4.1 Geometry of the Detection Electrodes 151 8.4.1.1 Embedded El.