Analytical Separation Science, 5 Volume Set

Leading the way for analytical chemists developing new techniques.

This new comprehensive 5 volume set on separation science provides a much needed research-level text for both academic users and researchers who are working with and developing the most current methods, as well as serving as a valuable resource for graduate and post-graduate students.

Comprising of five topical volumes it provides a comprehensive overview of the subject, highlighting aspects that will drive research in this field in the years to come.

Volume 1: Liquid Chromatography
Volume 2: Special Liquid Chromatography Modes and Capillary Electromigration Techniques
Volume 3: Gas, Supercritical and Chiral Chromatography
Volume 4: Chromatographic and Related Techniques
Volume 5: Sample Treatment, Method Validation, and Applications

Key Features:
- Comprises over 2,100 pages in 5 volumes – available in print and online
- Edited by an international editorial team which has both prominent and experienced senior researchers as well as young and dynamic rising stars
- Individual chapters are labeled as either introductory or advanced, in order to guide readers in finding the content at the appropriate level
- Fully indexed with cross referencing within and between all 5 volumes

About the Editors XVII

Preface XIX

List of Contributors XXI

Volume 1

1 Basic HPLC Theory and Definitions: Retention, Thermodynamics, Selectivity, Zone Spreading, Kinetics, and Resolution 1
Torgny Fornstedt, Patrik Forssén, and Douglas Westerlund

1.1 Basic Definitions 2

1.1.1 Basic Retention Models and Kinetics 6

1.1.2 Band Broadening and the Plate Height Concept 7

1.1.3 Sources of Zone Broadening 9

1.1.3.1 Eddy Diffusion 10

1.1.3.2 Molecular Diffusion 10

1.1.3.3 Slow Equilibration 10

1.1.4 Dependence of Zone Broadening on Flow Rate 11

1.2 Resolution 12

1.3 Modern Trends in Liquid Chromatography 14

1.3.1 Efficiency Trend 15

1.3.2 Permeability Trend 17

1.3.3 Selectivity and New Material Trend 19

1.4 Conclusions 21

References 22

2 Basic LC Method Development and Optimization 25
Victoria F. Samanidou

2.1 Introduction 25

2.2 Theoretical Aspects 26

2.2.1 Retention Factork 27

2.2.2 Selectivity α 27

2.2.3 Peak Asymmetry 27

2.2.4 Efficiency of Chromatographic Column and Theoretical Plates 27

2.2.5 Resolution Rs 28

2.2.6 The Fundamental vanDeemter Equation 29

2.3 Controlling Resolution 30

2.3.1 How to Improve N 32

2.3.1.1 Physical Characteristics of Packing Material 32

2.3.2 Increase ofk 33

2.3.3 Factors Influencing Selectivity or How to Improve α? 33

2.3.3.1 Optimization of Mobile-Phase Composition 34

2.3.3.2 pH Control, Ion-Pair Reagents, and Other Additives 35

2.3.3.3 Temperature 35

2.3.3.4 Stationary Phase and Column Selection 35

2.3.3.5 Stationary Phase and Packing Material Composition 36

2.4 Method Development Strategy 37

2.4.1 Gradient Elution versus Isocratic 38

2.4.2 Other Parameters in LC Method Development 38

2.5 Current and Future Trends 39

2.5.1 Two-Dimensional Chromatography 39

2.6 Conclusions 40

References 40

3 Recent Advances in Column Technology 43
Ross Andrew Shalliker and Danijela Kocic

3.1 Introduction 43

3.2 Column Packing: Downward Slurry Packing 45

3.3 Column Bed Heterogeneity 46

3.3.1 Axial Heterogeneity 46

3.3.2 Radial Heterogeneity and the Wall Effect 49

3.4 Active Flow Technology: A New Design Concept in Chromatography Columns 51

3.4.1 AFT Columns: Parallel Segmented Flow 51

3.4.2 AFT Columns: Curtain Flow 52

3.4.3 Performance of AFT Columns 53

3.4.3.1 Sensitivity 53

3.4.3.2 Efficiency 54

3.4.3.3 Speed 58

3.5 Summary 60

References 61

4 Hydrophilic Interaction Liquid Chromatography 63
Xinmiao Liang, Aijin Shen, and Zhimou Guo

4.1 Introduction 63

4.2 Separation Mechanism in HILIC 64

4.3 Stationary Phases for HILIC 67

4.3.1 Conventional NPLC Stationary Phases for HILIC 67

4.3.2 Stationary Phases Developed for HILIC 75

4.3.2.1 Polyaspartamide-Based Stationary Phases 75

4.3.2.2 Amide-Based Stationary Phases 75

4.3.2.3 Saccharides-Based Stationary Phases 76

4.3.2.4 Zwitterionic Stationary Phases 76

4.4 Application of HILIC 77

4.4.1 Application in the Pharmaceutical Field 77

4.4.2 Application in the Separation of Carbohydrates 78

4.4.3 Application in Proteome, Glycoproteome, and Phosphoproteome 78

4.4.4 Application in Metabolomics/Metabonomics 80

4.5 Conclusions and Outlook 81

References 81

5 LC–MS Interfaces 87
Pierangela Palma, Elisabetta Pierini, and Achille Cappiello

5.1 Introduction 87

5.2 API Sources 88

5.2.1 Electrospray Interface (ESI) 89

5.2.1.1 Principles of Operation and Ion Formation 90

5.2.1.2 Factors Influencing ESI Response 92

5.2.1.3 Modes of Operation 92

5.2.2 Atmospheric Pressure Chemical Ionization 93

5.2.2.1 Principles of Operation and Ion Formation 94

5.2.3 Atmospheric Pressure Photoionization 95

5.2.3.1 Principle of Operation 96

5.2.4 Atmospheric Pressure Laser Ionization 98

5.2.4.1 Principle of Operation and Ion Formation 98

5.3 Non-API Sources 99

5.3.1 Direct-EI 100

5.3.2 EI of Cold Molecules in Supersonic Molecular Beam (SMB) 103

5.3.3 Combined Single-Photon Low-Pressure Photoionization and EI Ionization 104

5.3.4 LC/DESI–MS Interface 106

References 107

6 LC–MS Applications in Environmental and Food Analysis 111
Alessandra Gentili, Fulvia Caretti, and Virginia Pérez Fernández

6.1 Introduction 111

6.2 Environmental Applications 112

6.2.1 Last Trends in Sample Preparation for LC–MS Analysis 112

6.2.2 Advances and Trends in Liquid Chromatography 113

6.2.3 Advances and Trends in Mass Spectrometry 113

6.3 Food Toxicant Applications 117

6.3.1 Recent Trends in Sample Preparation for LC–MS Analysis 117

6.3.2 Recent Trends in LC–MS Screening Analysis 118

6.3.3 Recent Trends in LC–MS Confirmatory Analysis 120

6.4 Foodomics as a Recent Approach Embracing Metabolomics, Proteomics, and Lipidomics 121

6.4.1 Food Proteomics 121

6.4.2 Food Metabolomics 124

6.4.3 Food Lipidomics 125

6.5 Trends and Future Developments 127

References 128

7 Solvents in Chromatography and Electrophoresis 135
Alain Berthod and Karine Faure

7.1 Introduction 135

7.2 Physicochemical Properties of Solvents 135

7.2.1 Melting and Boiling Points, and Vapor Pressure 135

7.2.2 Molecular Weight, Density, and Molar Volume 136

7.2.3 Viscosity, Surface Tension, UV Cutoff, and Refractive Index 136

7.2.4 Solvent Polarity Scales 137

7.2.5 New Solvents 142

7.3 Physicochemical Properties of Mixtures of Solvents 143

7.3.1 Fully Miscible Solvents 143

7.3.2 Nonfully Miscible Solvents and Phase Diagrams 144

7.3.3 Solvent Mixtures and Chromatographic Retention Times: Elution Strength 146

7.4 Mobile-Phase pH and Buffers 147

7.4.1 pH Definition 147

7.4.2 pH in Hydro-organic Mobile Phases 147

7.4.3 pKa Shifts in Hydro-organic Mobile Phases 148

7.5 Conclusions 151

Acknowledgments 157

References 157

8 Reversed Phase Liquid Chromatography 159
Maria C. García-Alvarez-Coque, Juan J. Baeza-Baeza, and Guillermo Ramis-Ramos

8.1 Introduction 159

8.2 The Stationary Phase 160

8.2.1 Silica Support and Chemical Bonding 161

8.2.2 Types of Phases 163

8.2.3 Silanol Effects 164

8.2.4 Silanol Deactivation 166

8.3 The Mobile Phase 167

8.3.1 Mobile Phase Components 167

8.3.2 Snyder’s Solvent Selectivity Triangle 168

8.3.3 Control of the Mobile-Phase pH 170

8.4 Temperature as Chromatographic Factor 172

8.5 Gradient versus Isocratic Elution 174

8.5.1 Solute Retention and Peak Width 174

8.5.2 Isocratic Elution 175

8.5.3 Gradients of Modifier: The Usual Solution for the General Elution Problem 175

8.5.4 Development of Gradients of Modifier 176

8.5.5 Strengths and Weaknesses of Gradients of Modifier 179

8.5.6 Other Types of Gradients 181

8.6 Attempts to Explain the Retention Mechanisms in RPLC 181

8.6.1 Solvent Adsorption and Partitioning in RPLC 181

8.6.2 The Solvophobic Theory 182

8.6.3 Solute Adsorption or Partitioning? 183

8.6.4 Investigating How RPLC Really Works 184

8.6.5 Going Down to the Molecular Detail 186

8.6.5.1 Chain Conformation 186

8.6.5.2 Adsorption and Partitioning of Common Solvents 186

8.6.5.3 Adsorption and Partitioning of Solutes 188

8.6.5.4 Anomalous Behavior with Highly Aqueous Mobile Phases 189

8.7 Development and Trends in RPLC 190

References 192

9 Modeling of Retention in Reversed Phase Liquid Chromatography 199
Maria C. García-Alvarez-Coque, Guillermo Ramis-Ramos, José R. Torres-Lapasió, and C. Ortiz-Bolsico

9.1 Introduction 199

9.2 Isocratic Elution 199

9.2.1 Polynomial Models to Describe Retention Using Modifier Content as a Factor 199

9.2.2 Polarity Models 201

9.2.3 pH as an Experimental Factor 202

9.3 Dead Time Estimation 206

9.3.1 Static Methods 207

9.3.2 Dynamic Methods 207

9.4 Effect of Temperature 209

9.4.1 Van’t Hoff Equation 209

9.4.2 Combined Effect of Modifier Content, pH, and Temperature 210

9.5 Effect of Pressure 211

9.5.1 Deviations of Retention Factors 211

9.5.2 Correction of Pressure Effects 212

9.6 Enhancing the Prediction of Retention 214

9.6.1 Practical Considerations 214

9.6.2 Influence of the Model Regression Process on the Quality of Predictions 215

9.7 Gradient Elution 216

9.7.1 Integration of the Fundamental Equation for Gradient Elution 216

9.7.2 Nonintegrable Retention Models 217

9.8 Computer-Assisted Interpretive Optimization 218

9.9 Stationary-Phase Characterization 220

9.9.1 Linear Solvation Energy Relationships 220

9.9.2 Local Models for Characterizing RPLC Columns 221

References 223

10 Normal-Phase and Polar Organic Solvents Chromatography 227
Ahmed A. Younes, Charlene Galea, Debby Mangelings, and Y. Vander Heyden

10.1 Introduction 227

10.2 HPLC Retention and Separation Mechanisms 228

10.2.1 Polarity-Based Separations 228

10.2.2 Charge-Based Separations 232

10.2.3 Size-Based Separations 232

10.2.4 Other Separation Mechanisms 232

10.3 Normal-Phase and Polar Organic Solvents Chromatography 233

10.3.1 Retention Mechanism 234

10.3.2 Stationary Phases 234

10.3.2.1 Nonbonded Phases 234

10.3.2.2 Bonded Phases 235

10.3.2.3 Stationary Phases and Selectivity 236

10.3.3 Mobile Phases 238

10.3.3.1 Mobile-Phase Selection 238

10.3.3.2 Solvent Strength and Selectivity 239

10.3.3.3 Isocratic and Gradient Elution 241

10.4 Conclusions 242

References 243

11 Inline Detectors 245
Ramisetti Nageswara Rao and Pothuraju Nageswara Rao

11.1 Introduction 245

11.2 Detector Characteristics 246

11.2.1 Sensitivity 246

11.2.2 Selectivity 246

11.2.3 Linearity 247

11.2.4 Dynamic Range 247

11.2.5 Detector Cell Volume 247

11.3 UV-Visible Absorbance Detector 247

11.3.1 Fixed Wavelength Detector 249

11.3.2 Variable Wavelength Detector 250

11.4 Photodiode Array Detector (PDA) 251

11.5 Fluorescence Detector 252

11.6 Refractive Index Detector (RID) 255

11.7 Evaporative Light-Scattering Detector 256

11.8 Electrochemical Detector 257

11.9 Charged Aerosol Detection 258

11.10 Conductivity Detector 259

11.11 Coupling Detectors 260

11.12 Comparison of HPLC Detectors 260

References 261

12 pH Effects on Chromatographic Retention Modes 263
Paweł Wiczling, Łukasz Kubik, and Roman Kaliszan

12.1 Introduction 263

12.2 pH Measurements of Mobile Phase 264

12.3 Effect of pH on Isocratic Retention 266

12.4 pH Effect on Organic Modifier Gradients 268

12.5 pH Gradient 269

12.6 Determination of pKa, log kw (Hydrophobicity), and S 274

12.7 Effect of pH in Normal-Phase Mode 275

12.8 Summary 277

References 277

13 Chemometrics in Data Analysis and Liquid Chromatographic Method Development 279
Biljana Jančic ́-Stojanovic ́and Tijana Rakic ́

13.1 Introduction 279

13.2 Chemometrics in Data Analysis 280

13.2.1 Data Preprocessing 280

13.2.2 Data Analysis 284

13.3 Chemometrics in LC Method Development 285

13.3.1 Analytical Target Profile and Critical Quality Attributes (Definition of the Objectives of the Method) 286

13.3.2 Quality Risk Assessment and Critical Process Parameters (Definition of Investigated Factors and Their Levels) 287

13.3.3 Investigation of the Knowledge Space (Selection of an Appropriate Experimental Design) 288

13.3.3.1 Screening Designs 289

13.3.3.2 Optimization Designs 291

13.3.4 Critical Quality Attributes Modeling (Creation of Mathematical Models) 293

13.3.5 Design Space 294

13.3.6 Selection of the Working Points 295

13.3.7 Robustness Testing 295

13.4 Conclusions 296

References 296

Index to Volume 1 I1-I18

Volume 2

Part One Special Liquid Chromatography Modes 299

1 Chiral Liquid Chromatography: Recent Applications with Special Emphasis on the Enantioseparation of Amino Compounds 301
István Ilisz

2 Chiral Separation of Some Classes of Pesticides by HPLC Method 321
Imran Ali, Iqbal Hussain, Mohd Marsin Sanagi, and Hassan Y. Aboul-Enein

3 Micellar Liquid Chromatography: Fundamentals 371
Maria C. García-Alvarez-Coque, Maria J. Ruiz-Angel, and Samuel Carda-Broch

4 Micellar Liquid Chromatography: Method Development and Applications 407
Maria C. García-Alvarez-Coque, Maria J. Ruiz-Angel, and Samuel Carda-Broch

5 Affinity Chromatography 461
Erika L. Pfaunmiller, Jesbaniris Bas, Marissa Brooks, Mitchell Milanuk, Elliott Rodriguez, John Vargas, Ryan Matsuda, and David S. Hage

6 Immunoaffinity Chromatography: Advantages and Limitations 483
Nancy E. Thompson and Richard R. Burgess

Part Two Capillary Electromigration Techniques 503

7 Capillary Electromigration Techniques: Capillary Electrophoresis 505
Václav Kašička

8 Modern Injection Modes (Stacking) for CE 531
Joselito P. Quirino

9 Capillary Gel Electrophoresis 555
Márta Kerékgyártó and András Guttman

10 Nonaqueous Capillary Electrophoresis 581
Julie Schappler and Serge Rudaz

11 Detectors in Capillary Electrophoresis 607
Petr Tůma and František Opekar

12 Trends in CE-MS and Applications 629
Anna Tycova and Frantisek Foret

13 Capillary Electrochromatography 653
Kai Zhang and Ruyu Gao

14 Micellar Electrokinetic Chromatography 675
Paolo Iadarola, Marco Fumagalli, and Simona Viglio

15 Chip-Based Capillary Electrophoresis 707
Yuanhong Xu, Jizhen Zhang and Jingquan Liu

16 Chiral Separations by Capillary Electrophoresis 731
E. Sánchez-López, M. Castro-Puyana, M.L. Marina, and A.L. Crego

Index to Volume 2 I1-I24

Volume 3

1 Gas Chromatography: Theory and Definitions, Retention and Thermodynamics, and Selectivity 775
Glenn E. Spangler

2 Basic Overview on Gas Chromatography Injectors 807
Md. Musfiqur Rahman, A.M. Abd El-Aty, and Jae-Han Shim

3 Basic Overview on Gas Chromatography Columns 823
Md. Musfiqur Rahman, A.M. Abd El-Aty, Jeong-Heui Choi, Ho-Chul Shin, Sung Chul Shin, and Jae-Han Shim

4 Overview of Detectors in Gas Chromatography 835
Md. Musfiqur Rahman, A.M. Abd El-Aty, and Jae-Han Shim

5 Current Use of Gas Chromatography and Applications 849
Walter Vetter

6 Gas Chromatography with Mass Spectrometry (GC-MS) 883
Walter Vetter

7 Chiral GC 927
Volker Schurig

8 New Essential Events in Modern Applications of Inverse Gas Chromatography 979
Adam Voelkel, Henryk Grajek, Beata Strzemiecka, and Katarzyna Adamska

9 Chip-Based Gas Chromatography 999
Hamza Shakeel and Masoud Agah

10 Portable Gas Chromatography 1021
Philip A. Smith

11 Packed Column Sub- and Supercritical Fluid Chromatography 1051
Caroline West, Syame Khater, and Eric Lesellier

12 Instrumentation for Sub- and Supercritical Fluid Chromatography 1075
Taghi Khayamian, Ali Daneshfar, and Hassan Ghaziaskar

Index to Volume 3 I1-I18

Volume 4

1 High-Performance Thin-Layer Chromatography 1093
Vicente L. Cebolla, Luis Membrado, Carmen Jarne, and Rosa Garriga

2 Field Flow Fractionation 1143
Gaëtane Lespes, Julien Gigault, and Serge Battu

3 Separations with a Liquid Stationary Phase: Countercurrent Chromatography or Centrifugal Partition Chromatography 1177
Alain Berthod and Karine Faure

4 Preparative Chromatography: Batch and Continuous 1207
José P.S. Aniceto and Carlos M. Silva

5 Fast and Miniaturized Chromatography 1315
Bárbara Socas-Rodríguez, Antonio V. Herrera-Herrera, Miguel Ángel González-Curbelo, Javier González-Sálamo, and Javier Hernández-Borges

6 Two-Dimensional Liquid Chromatography 1357
Morgan Sarrut, Nicola Marchetti, and Sabine Heinisch

Index to Volume 4 I1-I14

Volume 5

1 Sampling Strategies: Statistics of Sampling 1385
Małgorzata Bodnar, Piotr Konieczka, and Jacek Namieśnik

2 Targeted and Non-Targeted Analysis 1401
Luis E. Rodriguez-Saona, Marçal Plans Pujolras, and M. Monica Giusti

3 Conventional Extraction Techniques: Soxhlet and Liquid–Liquid Extractions and Evaporation 1437
Adegbenro Peter Daso and Okechukwu Jonathan Okonkwo

4 Main uses of Microwaves and Ultrasounds in Analytical Extraction Schemes: an Overview 1469
Idaira Pacheco-Fernández, Providencia González-Hernández, Priscilla Rocío-Bautista, María José Trujillo-Rodríguez, and Verónica Pino

5 Membrane-assisted Separations 1503
Jan Åke Jönsson

6 Dispersive Solid-Phase Extraction 1525
Bárbara Socas-Rodríguez, Antonio V. Herrera-Herrera, María Asensio-Ramos, and Javier Hernández-Borges

7 Solid-Phase Extraction 1571
Nil Ozbek, Asli Baysal, Suleyman Akman, and Mehmet Dogan

8 Solid-Phase Microextraction 1595
Ali Mehdinia and Mohammad Ovais Aziz-Zanjani

9 Liquid-Phase Microextraction 1625
Mohammad Reza Ganjali, Morteza Rezapour, Parviz Norouzi, and Farnoush Faridbod

10 Analytical Supercritical Fluid Extraction 1659
Julian Martínez and Ana Carolina de Aguiar

11 Extraction Methods Facilitated by the use of Magnetic Nanoparticles 1681
Priscilla Rocío-Bautista and Verónica Pino

12 Sample Derivatization in Separation Science 1725
Pascal Cardinael, Hervé Casabianca, Valerie Peulon-Agasse, and Alain Berthod

13 Validation of Analytical Methods Based on Chromatographic Techniques: An Overview 1757
Juan Peris-Vicente, Josep Esteve-Romero, and Samuel Carda-Broch

14 “Omics” and Biomedical Applications 1809
Pasquale Ferranti, Chiara Nitride, and Monica Gallo

15 Food Applications: Using Novel Sample Preparation Modes 1859
Mónica González and Venerando González

16 Forensic Applications 1877
Matías Calcerrada Guerreiro, María López-López, Ma Ángeles Fernández de la Ossa, and Carmen García-Ruiz

17 Environmental Applications of Solid Phase Microextraction Techniques 1897
Sarah Montesdeoca-Esponda, M Esther Torres-Padrón, Zoraida Sosa-Ferrera, and José Juan Santana-Rodríguez

Index to Volume 5 I1-I20

Index 1929

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