Sample Preparation in LC-MS Bioanalysis

Content: Intro --
Title Page --
Copyright Page --
Contents --
List of Contributors --
Preface --
List of Abbreviations --
Part I Current Sample Preparation Techniques in LC-MS Bioanalysis --
Chapter 1 Basic Sample Preparation Techniques in LC-MS Bioanalysis: Protein Precipitation, Liquid-Liquid Extraction, and Solid-Phase Extraction --
1.1 Introduction --
1.2 Physicochemical Properties of Drugs and Their Metabolites --
1.2.1 Hydrophilicity vs. Lipophilicity of Analyte(s) --
1.2.2 Protolytic Properties of Analyte(s) --
1.3 Pre-analytical Variables of Analyte(s) of Interest in Biological Matrix --
1.3.1 Stability --
1.3.2 Nonspecific Binding --
1.3.3 Protein Binding --
1.3.4 Blood-to-plasma Ratio and Red Blood Cell Partition --
1.4 Most Commonly Used Sample Preparation Methods in LC-MS Bioanalysis --
1.4.1 Protein Precipitation (PPT) --
1.4.1.1 Water-miscible Organic Solvents --
1.4.1.2 Acids --
1.4.2 Liquid-Liquid Extraction (LLE) --
1.4.2.1 Mechanism of LLE and Extraction Recovery --
1.4.2.2 Solvent in LLE --
1.4.2.3 General Procedures in LLE --
1.4.2.4 Application of LLE in LC-MS Bioanalysis --
1.4.2.5 Other Formats of LLE --
1.4.3 Solid-phase Extraction (SPE) --
1.4.3.1 SPE Stationary Phases (Sorbents) --
1.4.3.2 Common SPE Platforms in LC-MS Bioanalysis --
1.4.3.3 General SPE Workflows --
1.4.3.4 Other Formats of SPE --
1.4.4 Combination of PPT, LLE, and/or SPE in LC-MS Bioanalysis --
1.4.4.1 Combination of PPT and LLE --
1.4.4.2 Combination of PPT and SPE --
1.4.4.3 Combination of LLE and SPE --
1.4.5 Summary --
References --
Chapter 2 Online Extraction and Column Switching Techniques in LC-MS Bioanalysis --
2.1 Introduction --
2.2 System Configuration --
2.2.1 Single-column System --
2.2.2 Dual-column System --
2.2.3 Staggered Parallel Online Extraction Systems --
2.3 Commonly Used Online Extraction Techniques. 2.3.1 Turbulent/High Flow Chromatography --
2.3.2 Restricted Access Media --
2.3.3 Monolithic Materials --
2.3.4 Hydrophilic Interaction Liquid Chromatography --
2.3.5 Immunoaffinity Extraction --
2.3.6 Disposable Extraction Cartridges --
Online SPE --
2.3.7 Online Extraction of Dried Blood Spot (DBS) Samples --
2.3.8 SPE-MS --
2.4 Considerations for Utilizing Online Extraction Techniques --
2.4.1 Advantages and Limitations --
2.4.2 Strategies for Online Extraction Method Development --
2.5 Summary --
References --
Chapter 3 Equilibrium Dialysis, Ultracentrifugation, and Ultrafiltration in LC-MS Bioanalysis --
3.1 Introduction --
3.2 Challenges and Considerations --
3.3 Experimental Procedures --
3.3.1 Equilibrium Dialysis --
3.3.2 Ultrafiltration --
3.3.3 Ultracentrifugation --
3.4 Summary --
References --
Chapter 4 Phospholipid Depletion Techniques in LC-MS Bioanalysis --
4.1 Introduction --
4.2 Impact of Phospholipids on Bioanalytical Methods --
4.3 Investigating Matrix Effects Associated with Phospholipids --
4.4 Minimizing Matrix Effects Associated with Phospholipids --
4.4.1 Sample Dilution --
4.4.2 Column Manipulations --
4.4.3 Internal Standards --
4.4.4 Ionization Choice --
4.4.5 Other Experimental Modifications --
4.5 Removing Phospholipids Prior to LC-MS Analysis --
4.5.1 Protein Precipitations --
4.5.2 Liquid-Liquid Extraction and Supported Liquid Membranes --
4.5.3 Supported Liquid Extraction --
4.5.4 Electrostatic Removal --
4.5.5 Solid-Phase Extraction --
4.6 Example Methods that Demonstrate Successful Phospholipid Removal --
4.7 Conclusions --
Acknowledgement --
References --
Chapter 5 Salting-out Assisted Liquid-Liquid Extraction (SALLE) in LC-MS Bioanalysis --
5.1 Introduction --
5.2 Considerations in Developing a SALLE Method --
5.2.1 Salts --
5.2.2 Water-Miscible Solvent --
5.2.3 pH. 5.3 Combination of SALLE with Other Extraction Techniques --
5.4 Matrix Effect in SALLE --
5.5 Miniaturization and Automatization --
5.6 Summary --
References --
Chapter 6 Supported Liquid Extraction (SLE) in LC-MS Bioanalysis --
6.1 Introduction --
6.2 Principle of SLE --
6.3 Advantages and Limitation of SLE in Quantitative LC-MS Bioanalysis --
6.3.1 Advantages --
6.3.2 Limitation --
6.4 Key Consideration in Developing Robust SLE-LC-MS Bioanalytical Method --
6.5 Representative Protocols --
6.5.1 Material, Supplies, and Equipment --
6.5.2 Protocols for SLE Cartridge and Plate Processing --
6.6 Summary --
References --
Chapter 7 Immunocapture in LC-MS Bioanalysis --
7.1 Introduction --
7.2 Experimental Workflow and Optimization --
7.3 Considerations on the Selection of Capture Reagents and the Limitations --
7.4 Platforms for Immunocapture --
7.5 Internal Standard Selection --
7.6 Performance Evaluation --
7.7 Applications and Representative Protocols --
7.7.1 Endogenous Peptides/Proteins --
7.7.2 Protein-based Biotherapeutics --
7.7.3 Immunogenicity --
7.8 Validation Criteria and Regulatory Considerations --
7.9 Summary --
References --
Chapter 8 Microextraction Techniques in LC-MS Bioanalysis --
8.1 Introduction --
8.2 Solid-Phase Microextraction --
8.2.1 Conventional Fiber SPME --
8.2.2 Stir-Bar Sorptive Extraction --
8.2.3 Thin-Film Microextraction --
8.2.4 In-Tube SPME --
8.2.5 In-Needle SPME --
8.2.5.1 Solid-Phase Dynamic Extraction --
8.2.5.2 Microextraction by Packed Sorbent --
8.2.5.3 Fiber-Packed Needle Microextraction --
8.2.6 In-Tip SPME --
8.2.7 New Sorbents for SPME --
8.2.7.1 Monolithic Sorbent --
8.2.7.2 Carbon Nanotubes --
8.3 Liquid-Phase Microextraction --
8.3.1 Single-Drop Microextraction --
8.3.2 Hollow Fiber Liquid-Phase Microextraction --
8.3.3 Dispersive Liquid-Liquid Microextraction. 8.3.4 Influence Factors on LPME Efficiency --
8.4 Summary --
Acknowledgements --
References --
Chapter 9 Microsampling Applications with LC-MS Bioanalysis --
9.1 Introduction --
9.2 Plasma Microsampling Considerations --
9.2.1 Sample Collection --
9.2.2 Interaction with Thixotropic Gel --
9.2.3 Sample Manipulation --
9.2.4 Extraction, LC-MS/MS Analysis, and Detection --
9.3 Dried Blood (Matrix) Spot (DBS) Considerations --
9.3.1 Sample Collection --
9.3.2 Sample Manipulation --
9.3.3 Extraction, LC-MS/MS Analysis, and Detection --
9.4 Volumetric Absorptive Microsampling (VAMS) --
9.4.1 Sample Collection --
9.4.2 Sample Manipulation --
9.4.3 Extraction, LC-MS/MS Analysis, and Detection --
9.5 Emerging Techniques --
9.6 Summary --
Acknowledgements --
References --
Chapter 10 Nanomaterials for Sample Preparation in LC-MS Bioanalysis --
10.1 Introduction --
10.2 Carbon Nanomaterials --
10.3 Metallic NPs --
10.3.1 Metal Nanoparticles --
10.3.2 Metal Oxide Nanoparticles --
10.4 Nanoporous Materials --
10.4.1 Polymeric Nanomaterials --
10.4.2 Mesoporous Materials --
10.4.3 Molecular Imprinted Polymers (MIPs) --
10.5 Future Perspectives --
Acknowledgements --
References --
Chapter 11 Sample Preparation via Molecularly Imprinted Polymers (MIPs) in LC-MS Bioanalysis --
11.1 Introduction --
11.2 Preparation of MIPs --
11.2.1 Template and Monomer(s) --
11.2.2 Cross-linker --
11.2.3 Porogen --
11.3 MIPs for Sample Preparation in Bioanalysis --
11.3.1 Molecularly Imprinted Solid-phase Extraction (MISPE) --
11.3.1.1 Off-line Protocols --
11.3.1.2 Online Protocols --
11.3.1.3 In-line Protocols --
11.3.1.4 Other Protocols --
11.3.2 MIPs in Other Sample Preparation Techniques --
11.4 Fragment Imprinting --
11.5 Summary --
References --
Chapter 12 Stir-bar Sorptive Extraction for Sample Preparation in LC-MS Bioanalysis --
12.1 Introduction --
12.2 SBSE Principle. 12.3 SBSE Steps --
12.3.1 Extraction Procedure --
12.3.2 Desorption --
12.3.2.1 Thermal Desorption --
12.3.2.2 Liquid Desorption --
12.4 Derivatization --
12.4.1 In Situ Derivatization --
12.4.2 On-Stir-Bar Derivatization --
12.4.3 Post-Extraction Mode --
12.5 Coating Materials --
12.6 Applications --
12.7 Summary --
References --
Chapter 13 Monolithic Spin Column Extraction in LC-MS Bioanalysis --
13.1 Introduction --
13.2 History of Monoliths --
13.3 The Use of Monolith as Sorbent in Solid-Phase Extraction --
13.4 Monolithic Spin Column for Sample Preparation --
13.4.1 Extraction Procedure --
13.4.2 Extraction Mechanism --
13.4.3 Advantages and Limitations --
13.4.3.1 Zero Dead Volume --
13.4.3.2 No Channeling --
13.4.3.3 Ease of Operation --
13.4.3.4 Ease of Shape Modification --
13.4.3.5 Loading Sample Volume --
13.4.3.6 High Viscosity Sample --
13.4.3.7 Commercial Suppliers --
13.4.4 Applications --
References --
Chapter 14 Aptamer-based Sample Preparation in LC-MS Bioanalysis --
14.1 Introduction --
14.2 Aptamer-based Sample Preparation --
14.2.1 Aptamer-based Solid-phase Extraction --
14.2.1.1 Aptamer-based Affinity Columns for SPE --
14.2.1.2 Aptamer-based Magnetic SPE --
14.2.1.3 Aptamer-based Surface Affinity SPE --
14.2.1.4 Aptamer-functionalized Materials for Other SPE Format --
14.2.2 Aptamer-based Solid-phase Microextraction --
14.2.3 Aptamer-based Microfluidic Sample Preparation --
14.3 Representative Protocols --
14.4 Summary --
Acknowledgements --
References --
Chapter 15 Sample Extraction via Electromembrane in LC-MS Bioanalysis --
15.1 Introduction --
15.2 Factors Affecting the Extraction Efficiency of EME --
15.2.1 Composition of Supported Liquid Membrane and Nature of the Supports --
15.2.2 Composition of Acceptor and Donor (Sample) Phase --
15.2.2.1 For Extraction of Basic Drugs --
15.2.2.2 For Extraction of Acidic Drugs.