Analysis and Detection by Capillary Electrophoresis

Contributors to Voulme XLV......Page 1
Contents......Page 4
Series Editor\'s Preface......Page 13
Preface......Page 15
Introduction......Page 17
Electrophoretic mobility and electroosmotic flow......Page 18
Migration time, efficiency, and resolution......Page 20
Type and dimensions of capillaries......Page 22
Characteristics of the separation buffer (nature, concentration, pH and additives)......Page 23
Instrumentation......Page 27
Injection systems......Page 28
Capillaries......Page 30
Detection systems......Page 34
Separation Modes......Page 35
Hyphenated capillary electrophoretic techniques......Page 37
Role of CE techniques with respect to the analytical potential of other separation techniques......Page 39
Field of application of CE......Page 40
Trends......Page 43
References......Page 44
Introduction......Page 47
Fundamentals......Page 50
Parameters influencing the separation......Page 53
Development and optimization of a separation method......Page 54
Applications......Page 57
Separation principle......Page 61
Types of gels......Page 62
Applications......Page 64
Fundamentals......Page 66
Experimental procedure......Page 67
Applications......Page 70
Separation principle......Page 72
Coupling of CITP with other CE modes......Page 75
Electrokinetic chromatography......Page 76
Separation principle......Page 81
Efficiency......Page 83
Effect of the nature and concentration of the micelle......Page 84
Effect of pH......Page 86
Cyclodextrins (CD-MEKC)......Page 88
Organic modifiers......Page 89
Ion-pair reagents......Page 90
Applications......Page 91
Determination of solute-micelle association constants......Page 96
Estimation of the hydrophobicity of organic compounds......Page 97
Other pseudophases in EKC......Page 99
Cyclodextrin electrokinetic chromatography (CD-EKC)......Page 100
Microemulsion electrokinetic chromatography (MEEKC)......Page 105
Fundamentals......Page 111
Types of columns employed in CEC......Page 114
Instrumentation......Page 115
Theory......Page 116
Separation process......Page 117
Band broadening in CEC......Page 120
Mobile-phase considerations......Page 121
Applications......Page 123
Introduction......Page 124
Electrolytic solutions......Page 126
Analyte-additive interactions......Page 128
Methodological aspects......Page 130
Applications......Page 132
Acknowledgments......Page 134
References......Page 138
Introduction......Page 151
Basic principle of stacking......Page 153
Normal stacking mode......Page 155
Large-volume sample stacking......Page 156
Electrokinetic injection......Page 158
Sample stacking of analytes in micellar electrokinetic chromatography......Page 159
Stacking with reverse migrating micelles......Page 161
FESI with reverse migration micelles......Page 162
Principle of ITP......Page 163
Normal ITP-zone electrophoresis mode......Page 166
Transient ITP mode......Page 169
Principle of dynamic pH junction......Page 170
Outline placeholder......Page 0
Applications of dynamic pH junction......Page 174
Basic theory of sweeping......Page 175
Selective exhaustive injection-sweeping......Page 179
Dynamic pH junction sweeping......Page 180
Applications of Sweeping......Page 181
References......Page 182
Introduction......Page 189
Role of CFS–s......Page 190
Interfaces for coupling flow systems to CE......Page 191
CFSs to homemade CE arrangements......Page 192
Coupling flow systems to commercial CE equipments......Page 195
Flow injection-CE integrated microchips......Page 198
On-line clean-up and preconcentration......Page 201
Online extraction/filtering......Page 205
On-line dialysis......Page 206
On-line membrane and hollow fibre system......Page 208
On-line sample treatment and separations performed in auxiliary equipments......Page 210
Automatic calibration in CE through CFS......Page 216
Screening Flow Units-CE Analysis Arrangements......Page 220
Biomedical and pharmaceutical analysis......Page 223
Environmental analysis......Page 229
Food analysis......Page 232
Future prospects......Page 235
References......Page 236
Introduction......Page 240
Basic principles......Page 246
Detector design......Page 247
Light sources......Page 249
Optical system......Page 253
Ways for increasing the optical path length......Page 258
Data acquisition......Page 266
Diode-array detector......Page 268
Optimization of sensitivity......Page 269
Qualitative information......Page 271
Absorption imaging detection......Page 273
Derivatization and complexation procedures......Page 276
Indirect absorbance detection......Page 284
Thermal lens detection......Page 293
Photoacoustic detection......Page 302
UV-Vis absorbance detection in microchip electrophoresis......Page 306
References......Page 311
Objectives and outline of this chapter......Page 320
Basic concepts......Page 321
Light sources......Page 322
Optical train for LIF......Page 325
Excitation optics......Page 326
Detection cell......Page 327
Collinear arrangement......Page 328
Photomultiplier tubes......Page 329
Avalanche photodiodes (APDs)......Page 331
Imaging detectors: charge coupled devices (CCDs) and intensified charge coupled devices (ICCDs)......Page 332
Derivatization Methods......Page 335
Pre-capillary derivatization......Page 336
On-capillary derivatization......Page 341
Post-capillary derivatization......Page 343
Protein detection with and without derivatization......Page 344
Miniaturized Fluorescence Detection for Microchips......Page 350
On-chip fluorescence detection......Page 355
Confocal microscope......Page 356
Whole-chip detection......Page 357
Pigtail concept......Page 358
Integration of optical elements in microchips......Page 360
Background concepts: transfer ratio (TR) and dynamic reserve (DR)......Page 362
Choice of the background electrolyte (BGE): types of electrolyte additives used in indirect fluorescence detection......Page 364
Applications of indirect fluorescence detection......Page 366
Conclusions and Future Trends......Page 368
Multiphoton fluorescence detection......Page 372
Wavelength-resolved LIF detection......Page 374
Time-resolved LIF......Page 376
Selected Applications......Page 378
References......Page 379
Introduction......Page 390
Introduction......Page 391
Basic features of phosphorescence......Page 392
Quenched RTPL......Page 393
Coupling of phosphorescence detection to CE......Page 394
Applications in capillary zone electrophoresis......Page 395
Concluding remarks on CE-phosphorescence......Page 400
Development of CL detection in CE......Page 403
Luminol......Page 404
Acridinium ester......Page 406
Peroxyoxalate......Page 407
ECL......Page 408
On-column coaxial reactor......Page 409
Off-column coaxial reactor......Page 410
Luminol-based CL......Page 411
Peroxyoxalate-based CL......Page 416
Permanganate-based CL......Page 417
Miscellaneous CL reactions......Page 418
ECL......Page 420
Concluding remarks on CE-CL......Page 422
References......Page 423
Introduction......Page 427
Amperometry......Page 428
Voltammetry......Page 433
Conductivity......Page 435
Decoupling......Page 436
Applications......Page 438
Neurochemistry......Page 439
Biomarkers......Page 441
Environmental monitoring......Page 442
Conclusions and future prospects......Page 444
References......Page 445
Introduction......Page 455
Principles and instrumentation......Page 456
Electrospray ionization......Page 457
Sheathless......Page 458
Coaxial sheath flow......Page 460
Liquid junction......Page 464
Mass analyzers......Page 466
CE separation modes......Page 467
Micellar electrokinetic chromatography-mass spectrometry......Page 469
Capillary gel electrophoresis-mass spectrometry......Page 472
Capillary isoelectric focusing-mass spectrometry......Page 473
Capillary electrochromatography-mass spectrometry......Page 476
On-column transient isotachophoresis......Page 479
Buffers and solvents......Page 480
Partial filling technique......Page 482
Improving sensitivity in CE-MS......Page 485
Transient-capillary isotachophoresis......Page 486
Preconcentration devices......Page 487
Other procedures......Page 488
Chip-based CE-MS......Page 491
Proteins and peptides......Page 495
Drugs and metabolites......Page 501
Pesticides......Page 508
Other compounds......Page 512
Future outlook......Page 518
References......Page 519
ICP-MS fundamentals......Page 532
ICP-MS as detection system in hyphenated techniques......Page 535
Interfacing CE to ICP-MS: potentials and limitations......Page 537
The interface: key to success......Page 538
Considerations about sensitivity/detection limits in CE-ICP-MS......Page 542
The importance of the selected nebuliser in CE-ICP-MS couplings......Page 543
Concentric nebulisers......Page 544
Cross-flow nebulisers......Page 549
Ultrasonic nebulisers......Page 550
Micronebulisers......Page 551
Interfaces with micronebulisers and spray chamber......Page 553
Interfaces with just a micronebuliser (without spray chamber)......Page 556
CE-ICP-MS coupling via volatile species generation......Page 558
Interface designs based on VSG......Page 559
Strategies to improve sensitivity in CE-ICP-MS coupling......Page 561
Some selected contributions and applications......Page 563
References......Page 565
Introduction......Page 569
On-line MIR spectroscopic detection in CE......Page 570
FTIR spectroscopic detection in CE after solvent elimination......Page 575
Raman spectroscopy......Page 578
Raman scattering in CE......Page 579
Surface-enhanced Raman scattering in CE......Page 585
References......Page 592
Introduction......Page 595
NMR sensitivity improvements......Page 596
CE and NMR Hyphenation......Page 597
The size-matched NMR probe......Page 598
Interfacing CE to NMR......Page 602
CE-NMR measurements......Page 604
Applications......Page 609
CZE-NMR......Page 610
Sample concentration methods......Page 612
Diagnostic capabilities of CE/cITP-NMR......Page 619
Conclusions and Future Directions......Page 625
References......Page 626
Introduction......Page 629
Separation Modes in CE for Chiral Analysis......Page 634
Cyclodextrins......Page 635
Chiral crown ethers......Page 643
Macrocyclic antibiotics......Page 648
Proteins......Page 649
Ligand-exchange type selectors......Page 650
Capillary electrochromatography......Page 651
Non-aqueous capillary electrophoresis......Page 652
Improving the Detection Sensitivity for Chiral Analysis by CE......Page 657
On-line preconcentration techniques employed in chiral analysis by CE......Page 659
Alternative detection systems to on-line UV detection employed in chiral analysis by CE......Page 661
Pharmaceutical and biomedical analysis......Page 668
Enantiomeric separation of drugs......Page 669
Determination of the enantiomeric purity of drugs......Page 670
Quantitative chiral analysis of pharmaceutical preparations and biological samples......Page 676
Validation of chiral methods for the analysis of drugs......Page 678
Environmental analysis......Page 680
Enantiomeric separation of compounds of environmental interest......Page 681
Determination of the enantiomeric purity of agricultural formulations......Page 685
Monitoring the stereoselectivity of metabolic or (bio)degradation processes......Page 687
Enantiomeric separation of food components......Page 691
Determination of the enantiomeric purity of food components......Page 694
Chiral analysis of food samples......Page 695
Monitoring the stereoselectivity of food processing......Page 697
Other applications......Page 698
Chiral Analysis by Microchip Electrophoresis......Page 699
Future Perspectives......Page 701
References......Page 704
Introduction......Page 714
Principles and designs of capillary electrophoresis with electrochemical detection microsystems......Page 718
Material and microfabrication techniques......Page 719
Glass micromachining......Page 720
Polymer micromachining......Page 722
Fluids moving: principles of injection......Page 724
Detection implementation......Page 727
End-channel detection......Page 728
In-channel detection......Page 736
Off-channel detection......Page 737
Electrode materials......Page 741
Amperometry/voltammetry......Page 745
Conductimetry......Page 747
Neurotransmitters and related compounds......Page 752
Bioanalytical and clinical......Page 753
Environmental......Page 757
Conductimetry......Page 760
Conclusions and future directions......Page 763
References......Page 765
Symbol List......Page 770
Subject index......Page 772