Advances In Chromatography: Volume 44 (Advances in Chromatography)

Front Cover......Page 1
Foreword......Page 6
Contributors......Page 8
Table of Contents......Page 10
1 Separations in Multiple- Channel Microchips......Page 12
1.1 Introduction......Page 13
1.2.2 Polymer Substrates......Page 14
1.3.1 Rectilinear Microchip Designs......Page 15
1.3.2 Radial Microchip Designs......Page 17
1.4 Channel Filling and Sample Loading......Page 19
1.5 Injection Methods......Page 20
1.5.1 T-Type Injections......Page 21
1.5.2 Optically Gated Injection......Page 24
1.5.3 Capillary Sample Introduction......Page 26
1.6 Detection Methods......Page 28
1.6.2 Translation-Stage Confocal Detection......Page 29
1.6.3.2 Confocal Fluorescence Detection with a Rotary Scanner......Page 30
1.6.4 Fluorescence Detection with a Charge-Coupled Device (CCD)......Page 33
1.7 Applications of Multiple-Channel Microchips......Page 34
1.7.1.1 Separations Involving Restriction Enzyme Digests - DNA Fragment Analysis......Page 35
1.7.1.2 Genotyping......Page 36
1.7.1.3 Sequencing in Multiple-Channel Microchips......Page 38
1.7.2 Affinity Electrophoresis for Immunoassays in Microchips......Page 40
1.7.3.1 Application to DNA......Page 41
1.8 Conclusions and Future Perspectives......Page 43
References......Page 46
Abstract......Page 56
2.2 Temperature Effects on Retention and Selectivity......Page 57
2.3.1 Columns and Stationary Phases......Page 60
2.3.2 Temperature Programming and Instrumentation......Page 62
2.3.3 Applications......Page 63
2.4.1 Columns and Stationary Phases......Page 67
2.4.2 Temperature Programming and Instrumentation......Page 74
2.4.3 Applications......Page 76
References......Page 77
3 Lipophilicity Measurements by Liquid Chromatography......Page 90
3.1 Introduction......Page 91
3.3 The Uses of Lipophilicity......Page 92
3.4 logP, logD, and Other Terms for Expressing Lipophilicity......Page 93
3.5 The Effect of Chemical Reactions on Partitioning......Page 94
3.6 Octanol and Other Partition Solvents......Page 98
3.7 Calculations Involving logP......Page 101
3.8 logP Measurement by Shake-Flask......Page 102
3.9 Lipophilicity Measurement by High- Performance Liquid Chromatography (HPLC)......Page 105
3.9.1 HPLC with Octanol-Coated Columns......Page 107
3.9.2 ELogP Method......Page 111
3.9.5 The extrapolation method, logkw......Page 113
3.9.6 Isocratic logk Values......Page 116
3.9.7 The Significance of Slope S......Page 117
3.9.8 Correction for Ionization......Page 118
3.9.9 The Influence of Stationary Phase on Lipophilicity Measurements......Page 119
3.9.10.1 Organic Modifier......Page 123
3.9.10.3 Ionic Strength......Page 125
3.9.10.4 Masking Agents......Page 126
3.9.10.7 The Effect of Temperature......Page 127
3.9.11 Chromatographic Hydrophobicity Index (CHI)......Page 128
3.9.12 Abraham-Type Equations for RP-HPLC......Page 136
3.10 Lipophilicity Estimation by Thin-Layer Chromatography......Page 138
3.10.1 Relationship between RM and Molar Fraction X of the Organic Modifier in the Mobile Phase......Page 139
3.10.2 Influence of pH......Page 142
3.10.3 Influence of Mobile Phase Composition on RM0 Value......Page 143
3.10.4 Influence of Stationary Phase on RM0 Value......Page 144
3.10.5 Specific Hydrophobic Surface Area of the Solute......Page 145
3.10.6 Relationship between Intercepts (RM0) and Slopes (a1)......Page 146
3.10.7 RM Determination and Correlation with Partition Coefficients, logP......Page 154
3.11 Chromatographic Determination of Hydrophilic-Lipophilic Balance......Page 156
3.11.1 Drug Lipophilicity......Page 157
3.11.2 Miscellaneous......Page 159
3.11.3 Studies using Both RP-HPLC and RP-HPTLC......Page 160
3.12.1 Micellar Liquid Chromatography (MLC)......Page 165
3.12.2 Reversed-Phase Ion Pair Chromatography (RP-IPC)......Page 166
3.12.3 Countercurrent Chromatography (CCC)......Page 167
Glossary......Page 168
References......Page 169
4 Concepts and Practice of Multidimensional High- Performance Liquid Chromatography......Page 188
4.1 INTRODUCTION......Page 189
4.1.2 Solvent Selectivity......Page 190
4.1.3 Stationary Phase Selectivity......Page 191
4.1.4 Temperature Selectivity......Page 193
4.2 One-Dimensional Separations......Page 195
4.3.1 Assessment of the Separation Potential......Page 196
4.3.1.1 SMO Treatment of the Two-Dimensional Approach......Page 197
4.4 Types of Chromatographic Separation Displacements......Page 199
4.5 Two-Dimensional Chromatographic Systems......Page 202
4.6 Sample Dimensionality......Page 203
4.7 Orthogonality in Two-Dimensional Liquid Chromatography......Page 204
4.7.1 Determination of Orthogonality for Two-Dimensional Separations......Page 206
4.7.2.1 Correlation Coefficients and Color Maps......Page 208
4.7.2.2 Principle Component Analysis......Page 210
4.7.2.3 Information Theory......Page 211
4.7.2.4 Geometric Approach to Factor Analysis......Page 213
4.7.2.5 Combination Methods......Page 215
4.8 Application of Multidimensional Liquid Chromatography......Page 219
4.8.1 Designing Two-Dimensional Separations in Accordance with the Findings of Orthogonality Studies......Page 223
4.8.3 Two-Dimensional System Design......Page 226
4.8.4 Dual- and Quad-Column Second-Dimension Designs......Page 229
4.9 Anomalies in Multidimensional Separations......Page 235
4.10 Conclusion......Page 237
REFERENCES......Page 239
5 High-Performance Liquid Chromatography in the Pharmaceutical Industry: Application, Validation, and Regulatory Issues Under the PAT Framework......Page 248
5.2 Process Analytical Initiative......Page 249
5.2.2 Process Analytical Tools......Page 251
5.2.3 Process and Endpoint Monitoring and Control Tools......Page 253
5.3 Method Validation......Page 254
5.3.1 Precision......Page 256
5.3.4 Limit of Quantitation......Page 257
5.3.7 Linearity......Page 258
5.3.8 System Suitability......Page 259
5.4.1 Installation Qualification (IQ)......Page 260
5.5 Electronic Records and Signatures......Page 261
REFERENCES......Page 263
6.1 Introduction......Page 268
6.2 Mechanisms of Selectivity......Page 271
6.2.1 Effect of Side Chain Substitutions......Page 273
6.2.2 Spectroscopic and Thermal Studies......Page 274
6.2.3 Analyte Structure Effects......Page 275
6.2.5 Mobile Phase Effects......Page 276
6.3.1 Normal-Phase Mode......Page 278
6.3.2 Polar Organic Mode......Page 279
6.3.3 Reversed-Phase Mode......Page 285
6.3.4 Supercritical Fluid Chromatography......Page 286
6.4 Mobile Phase Additives......Page 289
6.5 Conclusions......Page 294
REFERENCES......Page 295
7.1 Introduction......Page 302
7.2 Chaotropic Effect......Page 303
7.3 Chaotropic Model......Page 306
7.4 Effect of Different Counteranions......Page 308
7.5 Retention of the Counteranions......Page 309
7.6 Effect of the Counterion Type and Concentration on Peak Efficiency and Asymmetry......Page 312
7.7 Applications in the Pharmaceutical Industry......Page 315
7.8 Concluding Remarks......Page 323
References......Page 324
8.1 Introduction......Page 328
8.3 High Levels of Organic Solvents with Water-Soluble Proteins......Page 329
8.4 High Levels of Organic Solvents with Water-Insoluble Proteins......Page 334
References......Page 338
D......Page 342
I......Page 343
L......Page 344
N......Page 345
R......Page 346
T......Page 347
X......Page 348