NANOCHROMATOGRAPHY AND NANOCAPILLARY ELECTROPHORESIS NANOCHROMATOGRAPHY AND NANOCAPILLARY ELECTROPHORESIS Pharmaceutical and Environmental Analyses IMRAN ALI HASSAN Y. ABOUL-ENEIN VINOD K. 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Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynot beavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteatwww. wiley.com. LibraryofCongressCataloging-in-PublicationData: Ali,Imran. Nanochromatographyandnanocapillaryelectrophoresis:pharmaceuticalandenvironmental analyses/ImranAli,HassanY.Aboul-Enein,VinodK.Gupta. p.;cm. Includesbibliographicalreferencesandindex. ISBN978-0-470-17851-5(cloth) 1. Chromatographicanalysis. 2. Capillaryelectrophoresis. 3. Drugs—Analysis. 4. Pollutants—Analysis. 5. Environmentalpollutants—Analysis. 6. Nanoparticles—Analysis. I.Aboul-Enein,HassanY. II.Gupta,VinodKumar,1953– III.Title. [DNLM: 1. Nanotechnology—methods. 2. Electrophoresis,Capillary—methods. 3. EnvironmentalPollutants—analysis. 4. PharmaceuticalPreparations—analysis. QT36.5A398n2009] QP519.9.C47A452009 5430.8—dc22 2008033275 PrintedintheUnitedStatesofAmerica 10 9 8 7 6 5 4 3 2 1 To the memories of my late parents: Basheer Ahmed and Mehmudan Begum. I. A. To my wife, Nagla, whose love and devotion have been an inspiration to me. H. Y. A.-E. To the memoryof my late father Sri Jeewan Lal Gupta who has been my mentorall through. V. K.G. CONTENTS PREFACE xiii ACKNOWLEDGMENTS xv 1 Introduction 1 1.1. Nanoanalyses / 1 1.2. Definition of Nanochromatographyand Nanocapillary Electrophoresis / 2 1.3. Nanochromatographyand Nanocapillary Electrophoresis / 3 1.4. Fabrication of Microdevices / 4 1.5. Developments in Nanoanalyses / 6 1.6. Data Integration / 7 1.7. Protocol of Nanoanalyses / 10 1.8. Scope of the Book / 12 1.9. Conclusion / 12 References / 12 2 Fabrication of Microchips 17 2.1. Introduction / 17 2.2. Substrates / 18 vii viii CONTENTS 2.3. Techniques of Fabrication / 20 2.3.1. Glass Chips / 22 2.3.2. Quartz Chips / 28 2.3.3. Silica Chips / 31 2.3.4. Polymer Chips / 34 2.3.5. Plastic Chips / 36 2.3.6. Chips and the Polymerase Chain Reaction / 37 2.4. Surface Modification / 39 2.4.1. Modification by Polymers / 40 2.4.2. Modification by Silica Gel / 42 2.4.3. Modification by Monolithics / 44 2.4.4. Modification by Sulfonation / 44 2.5. Designs of Chips / 45 2.6. Bindings in Chips / 49 2.7. Conclusion / 50 References / 51 3 Instrumentation of Nanochromatography and Nanocapillary Electrophoresis 59 3.1. Introduction / 59 3.2. Nanoliquid Chromatography (NLC) / 60 3.2.1. Mobile Phase Reservoirs / 62 3.2.2. Mobile Phases and Flow Calibration / 62 3.2.3. Mobile Phase Tubings / 63 3.2.4. Solvent Delivery Pump / 64 3.2.5. Sample Injector / 66 3.2.6. Separation Chips / 68 3.2.7. Detectors / 70 3.2.8. Recorder / 71 3.2.9. Sample Preparation Units / 72 3.3. Nanocapillary Electrophoresis / 74 3.3.1. Separation Chip / 76 3.3.2. Background Electrolyte and Its Reservoirs / 79 3.3.3. Sample Injection Port / 79 3.3.4. Detectors / 82 CONTENTS ix 3.3.5. Recorder / 83 3.3.6. Sample Preparation Units / 83 3.4. Conclusion / 85 References / 86 4 Detection in Nanochromatography and Nanocapillary Electrophoresis 91 4.1. Introduction / 91 4.2. Mass Spectrometer Detectors / 92 4.3. Fluorescence Detectors / 97 4.4. Electrochemical Detectors / 99 4.5. Element Specific Detectors / 101 4.6. Miscellaneous Detectors / 103 4.7. Conclusion / 105 References / 105 5 Sample Preparation in Nanochromatography and Nanocapillary Electrophoresis 109 5.1. Introduction / 109 5.2. Sample Preparation / 111 5.3. Sampling / 111 5.3.1. Biological Samples / 111 5.3.1.1. Blood / 112 5.3.1.2. Urine / 112 5.3.1.3. Tissues / 112 5.3.1.4. Plants / 113 5.3.1.5. Food Stuffs / 113 5.3.2. Environmental Samples / 113 5.3.2.1. Air / 113 5.3.2.2. Water / 114 5.3.2.3. Sediment and Soils / 115 5.4. Preservation / 115 5.5. Filtration / 116 5.6. Digestion/Homogenization / 118 5.7. Extractions / 119 5.8. Clean Up / 119 5.9. Preconcentration / 121 x CONTENTS 5.10. Off-Line Nanosample Preparation Methods / 121 5.10.1. Nano Solid Phase Extractions / 121 5.10.2. Nano Membrane Extractions / 123 5.10.3. Nano Miscellaneous Extractions / 124 5.11. Online Nanosample Preparation Methods / 125 5.12. Conclusion / 138 References / 138 6 Nano-High Performance Liquid Chromatography 145 6.1. Introduction / 145 6.2. Nano-HPLC / 146 6.3. Applications / 146 6.3.1. Nano-HPLCof Biological Matrices / 146 6.3.1.1. Proteomics / 147 6.3.1.2. Drugs Development and Design / 151 6.3.1.3. Environmental Analysis / 155 6.4. Optimization of Separations in Nano-HPLC / 161 6.5. Troubleshooting in Nano-HPLC / 161 6.6. Conclusion / 161 References / 162 7 Nanocapillary Electrochromatography and Nanomicellar Electrokinetic Chromatography 167 7.1. Introduction / 167 7.2. Nanocapillary Electrochromatography / 167 7.2.1. Biological Samples / 168 7.2.2. Environmental Samples / 177 7.2.3. Mechanism of Separation / 181 7.3. Nanomicellar Electrokinetic Chromatography / 181 7.3.1. Biological Samples / 182 7.3.2. Environmental Samples / 184 7.3.3. Mechanisms of Separation / 187 7.4. Conclusion / 188 References / 188 CONTENTS xi 8 Nanocapillary Electrophoresis 191 8.1. Introduction / 191 8.2. Optimization / 192 8.3. Applications / 200 8.3.1. Proteomics / 200 8.3.2. Genomics / 205 8.3.3. Amino Acids / 210 8.3.4. Drug Development and Design / 211 8.3.5. Enzymes and Hormones / 214 8.3.6. Biological Fluids / 218 8.3.7. Foods and Beverages / 221 8.3.8. Viruses and Bacteria / 224 8.3.9. Explosives / 226 8.3.10. Environmental Analyses / 228 8.3.11. Miscellaneous Applications / 232 8.4. Mechanism of Separation / 234 8.5. Conclusion / 234 References / 235 9 Chiral Separations by Nanoliquid Chromatography and Nanocapillary Electrophoresis 245 9.1. Introduction / 245 9.2. Nanoliquid Chromatography / 246 9.3. Nanocapillary Electrophoresis / 249 9.4. Mechanisms of Chiral Separation / 260 9.5. Conclusion / 261 References / 261 10 Perspectives on Nanoanalyses 263 10.1. Introduction / 263 10.2. Future of Microfluidic Devices / 264 10.3. Future Challenges / 265 10.4. Conclusion / 266 References / 267 Subject Index 269
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