Sample Preparation in LC-MS Bioanalysis

WENKUI LI is a Senior Fellow at the Novartis Institutes for BioMedical Research Pharmacokinetic Sciences. He serves on the Editorial Board of Biomedical Chromatography. WENYING JIAN is a Senior Principal Scientist in Janssen Research and Development at the Johnson & Johnson Company. She serves on the Editorial Board of Journal of Pharmacological and Toxicological Methods. YUNLIN FU is an Investigator at the Novartis Institutes for BioMedical Research Pharmacokinetic Sciences.

"A welcome reference which provides a complete overview of current and new approaches in sample preparation for LC-MS...To have an exhaustive compilation of strategies with “practical tips and tricks” can only be inspiring for the readers helping him to make the best choice for his specific challenge." Gérard Hopfgartner, Analytical and Bioanalytical Chemistry, January 2020

• List of Contributors xviPreface xxList of Abbreviations xxiiPart I Current Sample Preparation Techniques in LC‐MS Bioanalysis 11 Basic Sample Preparation Techniques in LC‐MS Bioanalysis: Protein Precipitation, Liquid–Liquid Extraction, and Solid‐Phase Extraction 3Wenkui Li, Wenying Jian, and Yunlin Fu1.1 Introduction 31.2 Physicochemical Properties of Drugs and Their Metabolites 41.3 Pre‐analytical Variables of Analyte(s) of Interest in Biological Matrix 51.4 Most Commonly Used Sample Preparation Methods in LC‐MS Bioanalysis 7References 272 Online Extraction and Column Switching Techniques in LC‐MS Bioanalysis 31Yan Mao and Mike (Qingtao) Huang2.1 Introduction 312.2 System Configuration 322.3 Commonly Used Online Extraction Techniques 332.4 Considerations for Utilizing Online Extraction Techniques 402.5 Summary 41References 423 Equilibrium Dialysis, Ultracentrifugation, and Ultrafiltration in LC‐MS Bioanalysis 45Theo de Boer and Henri Meijering3.1 Introduction 453.2 Challenges and Considerations 463.3 Experimental Procedures 463.4 Summary 49References 514 Phospholipid Depletion Techniques in LC‐MS Bioanalysis 52Stacy Brown and Jennifer Carmical4.1 Introduction 524.2 Impact of Phospholipids on Bioanalytical Methods 524.3 Investigating Matrix Effects Associated with Phospholipids 554.4 Minimizing Matrix Effects Associated with Phospholipids 564.5 Removing Phospholipids Prior to LC‐MS Analysis 574.6 Example Methods that Demonstrate Successful Phospholipid Removal 604.7 Conclusions 63Acknowledgement 64References 645 Salting‐out Assisted Liquid–Liquid Extraction (SALLE) in LC‐MS Bioanalysis 68Jun Zhang and Xin Xiong5.1 Introduction 685.2 Considerations in Developing a SALLE Method 685.3 Combination of SALLE with Other Extraction Techniques 725.4 Matrix Effect in SALLE 725.5 Miniaturization and Automatization 735.6 Summary 73References 736 Supported Liquid Extraction (SLE) in LC‐MS Bioanalysis 76Zhongzhe Cheng and Hongliang Jiang6.1 Introduction 766.2 Principle of SLE 766.3 Advantages and Limitation of SLE in Quantitative LC‐MS Bioanalysis 776.4 Key Consideration in Developing Robust SLE‐LC‐MS Bioanalytical Method 796.5 Representative Protocols 806.6 Summary 81References 827 Immunocapture in LC‐MS Bioanalysis 85Ang Liu7.1 Introduction 857.2 Experimental Workflow and Optimization 857.3 Considerations on the Selection of Capture Reagents and the Limitations 867.4 Platforms for Immunocapture 897.5 Internal Standard Selection 897.6 Performance Evaluation 907.7 Applications and Representative Protocols 917.8 Validation Criteria and Regulatory Considerations 947.9 Summary 95References 958 Microextraction Techniques in LC‐MS Bioanalysis 98Marcio Rodrigues, Ana Fortuna, Amilcar Falcao, and Gilberto Alves8.1 Introduction 988.2 Solid‐Phase Microextraction 998.3 Liquid‐Phase Microextraction 1088.4 Summary 113Acknowledgements 113References 1139 Microsampling Applications with LC‐MS Bioanalysis 117Chester L. Bowen and Matthew Barfield9.1 Introduction 1179.2 Plasma Microsampling Considerations 1189.3 Dried Blood (Matrix) Spot (DBS) Considerations 1219.4 Volumetric Absorptive Microsampling (VAMS) 1239.5 Emerging Techniques 1259.6 Summary 126Acknowledgements 126References 12610 Nanomaterials for Sample Preparation in LC‐MS Bioanalysis 128Rodrigo A. Gonzalez‐Fuenzalida, Neus Jornet‐Martinez, Rosa Herraez‐Hernandez, and Pilar Campins‐Falco10.1 Introduction 12810.2 Carbon Nanomaterials 12810.3 Metallic NPs 13310.4 Nanoporous Materials 13510.5 Future Perspectives 136Acknowledgements 136References 13711 Sample Preparation via Molecularly Imprinted Polymers (MIPs) in LC‐MS Bioanalysis 139Myriam Diaz‐Alvarez and Antonio Martin‐Esteban11.1 Introduction 13911.2 Preparation of MIPs 13911.3 MIPs for Sample Preparation in Bioanalysis 14211.4 Fragment Imprinting 14711.5 Summary 147References 14712 Stir‐bar Sorptive Extraction for Sample Preparation in LC‐MS Bioanalysis 152Maria Kechagia, Maria Kissoudi, and Victoria F. Samanidou12.1 Introduction 15212.2 SBSE Principle 15312.3 SBSE Steps 15412.4 Derivatization 15512.5 Coating Materials 15612.6 Applications 15812.7 Summary 161References 16113 Monolithic Spin Column Extraction in LC‐MS Bioanalysis 163Akira Namera and Takeshi Saito13.1 Introduction 16313.2 History of Monoliths 16313.3 The Use of Monolith as Sorbent in Solid‐Phase Extraction 16413.4 Monolithic Spin Column for Sample Preparation 165References 17114 Aptamer‐based Sample Preparation in LC‐MS Bioanalysis 174Fuyou Du, Zongyu Wei, Qiulian Zeng, and Guihua Ruan14.1 Introduction 17414.2 Aptamer‐based Sample Preparation 17514.3 Representative Protocols 18114.4 Summary 185Acknowledgements 185References 18515 Sample Extraction via Electromembrane in LC‐MS Bioanalysis 188Maria Ramos‐Payan, Rut Fernandez‐Torres, and Miguel Angel Bello‐Lopez15.1 Introduction 18815.2 Factors Affecting the Extraction Efficiency of EME 19015.3 Recent Developments in EME 19115.4 Bioanalytical Applications 19315.5 Summary 197References 197Part II Matrix‐specific Sample Preparation Techniques in LC‐MS Bioanalysis 20116 Tissue Sample Preparation in LC‐MS Bioanalysis 203Hong Gao and John Williams16.1 Introduction 20316.2 Selection of Homogenization Method 20316.3 Common Protocols 20916.4 Protocols for Special Tissue Sample Preparation 21016.5 Challenges Associated with Tissue Homogenization 21216.6 Summary 214References 21417 Sample Preparation for LC‐MS Bioanalysis of Peripheral Blood Mononuclear Cells 217Yunlin Fu and Wenkui Li17.1 Introduction 21717.2 Peripheral Blood Mononuclear Cells (PBMCs) 21717.3 Sample Preparation Workflow for LC‐MS Bioanalysis of PBMC Samples 21717.4 Representative Protocols 22017.5 Summary 222References 22218 Sample Preparation for LC‐MS Bioanalysis of Urine, Cerebrospinal Fluid, Synovial Fluid, Sweat, Tears, and Aqueous Humor Samples 225Allena J. Ji18.1 Introduction 22518.2 Sample Preparation Methods for Urine 22518.3 Sample Preparation Methods for Cerebrospinal Fluid 23018.4 Sample Preparation Methods for Synovial Fluid 23118.5 Sample Preparation Methods for Sweat 23118.6 Sample Preparation Methods for Tears 23418.7 Sample Preparation Methods for Aqueous Humor 23618.8 Summary 236References 23619 Sample Preparation for LC‐MS Bioanalysis of Liposomal Samples 238Wenying Jian, Rao N.V.S. Mamidi, and Naidong Weng19.1 Introduction 23819.2 Major Types of Sample Extraction Techniques for Liposomal Samples 23919.3 Key Considerations in Sample Preparation for Liposomal Samples 24219.4 Typical Protocols 24519.5 Summary 246References 246Part III Sample Preparation Techniques for LC‐MS Bioanalysis of Challenging Molecules 24920 Key Pre‐analytical Considerations in LC‐MS Bioanalysis 251Fumin Li, Bruce J. Hidy, and Rand G. Jenkins20.1 Introduction 25120.2 The Pre‐analytical Phase 25120.3 Bioanalytical Evaluation‐planning 25320.4 Common Pre‐analytical Issues in LC‐MS Bioanalysis 25520.5 Summary 258References 25921 Derivatization in Sample Preparation for LC‐MS Bioanalysis 260Dafang Zhong and Yunting Zhu21.1 Introduction 26021.2 Derivatization Strategies 26021.3 Key Considerations for Derivatization 26421.4 Application of Derivatization for Quantitative LC‐MS Bioanalysis 26521.5 Summary 270References 27122 Sample Preparation for LC‐MS Bioanalysis of Lipids 275Samuel Hofbauer, Ashkan Salamatipour, Ian A. Blair, and Clementina Mesaros22.1 Introduction 27522.2 Sample Preparation for LC‐MS Bioanalysis of Lipids 27522.3 Case Studies of LC‐MS Bioanalysis of Lipids 28022.4 Summary 281References 28223 Sample Preparation for LC‐MS Bioanalysis of Peptides 284Long Yuan23.1 Introduction 28423.2 Properties of Peptides and Sample Pretreatment 28523.3 Sample Preparation Strategies 28723.4 Conclusions 296Acknowledgements 297References 29724 Sample Preparation for LC‐MS Bioanalysis of Proteins 304Nico van de Merbel24.1 Introduction 30424.2 Intact Versus Digested Protein Analysis 30524.3 Enzymatic Digestion 30624.4 Protein Depletion 30824.5 Protein Extraction (Before Digestion) 30824.6 Peptide Extraction (After Digestion) 31224.7 Combined Protein and Peptide Extraction 31424.8 Summary 314References 31525 Sample Preparation for LC‐MS Bioanalysis of Oligonucleotides 319Michael G. Bartlett, Jaeah Kim, Babak Basiri, and Ning Li25.1 Introduction 31925.2 Properties of Oligonucleotides and Associated Challenges in LC‐MS Bioanalysis 31925.3 Classes of Oligonucleotides 32225.4 Major Types of Sample Extraction Techniques 32325.5 Key Considerations in Sample Preparation for LC‐MS Bioanalysis of Oligonucleotides 32725.6 Representative Protocols 32825.7 Summary 330References 33026 Sample Preparation for LC‐MS Bioanalysis of Antibody–Drug Conjugates 335Cong Wei and Ragu Ramanathan26.1 Introduction 33526.2 Properties of ADC and Challenges for Sample Preparation 33526.3 Sample Preparation Methods and Common Protocols 34226.4 Future Perspective 347Acknowledgements 348References 348Index 351