Hydrophillic Interaction Liquid Chromatography (Hilic) and Advanced Applications

Hydrophilic Interaction Liquid Chromatography HILIC And Advanced Applications......Page 1
Chromatographic Science Series......Page 2
Hydrophilic Interaction Liquid Chromatography hilic And Advanced Applications......Page 6
Contents......Page 8
Preface......Page 11
Editors......Page 12
Contributors......Page 14
Contents......Page 18
1.1 Fundamental Features of Aqueous Normal- Phase Retention......Page 19
1.2.1 ANP 1......Page 20
1.2.2 ANP 2......Page 21
1.2.3 ANP 3......Page 23
1.3.2 Temperature Behavior......Page 24
1.3.3 Repeatability......Page 26
1.3.4 Re-Equilibration......Page 27
1.4.2 Organic Component of Mobile Phase......Page 28
1.4.3 Mobile Phase Additive......Page 29
1.4.4 Sample Solvent Additive......Page 30
1.4.5 Gradients......Page 31
1.5.1 Amino Acids......Page 32
1.5.2 Carbohydrates......Page 33
1.5.3 Organic Acids......Page 34
1.5.4 Nucleotides......Page 37
1.5.5 Other Analytes......Page 39
Acknowledgment......Page 42
References......Page 43
2.1 Introduction......Page 44
2.2 Theoretical Introduction and Definitions......Page 46
2.3 Experimental Design......Page 49
2.4.1 Relationship between Experimentally Determined K\' and calculated log Dph3.0\r......Page 51
2.4.2 Discussion of Assumpt ions Made to Formulate Hypothesis......Page 52
2.5 Conclusions......Page 60
References......Page 61
Contents......Page 63
3.2.1 Introduction......Page 64
3.2.3 Column Chemistry......Page 65
3.3.1 Introduction......Page 66
3.3.2 Column Chemistry......Page 67
3.3.3 Separation Mechanism......Page 68
3.3.4 Applications......Page 69
3.4 HILI C Behavior of Reversed- Phase/ Ion- Exchange Mixed- Mode Stationary Phases......Page 71
3.4.1 Retent ion Behavior of Xanthins, Nucleosides, an d Wate r-Soluble Vitamins on RP/WAX Mixed-Mode Columns in HILIC Mode......Page 72
3.4.2 Retention Behavior of Fungal Metabolite s on RP/WAX Mixed-Mode Columns in HILIC Mode......Page 73
3.4.3 HILIC Behavior Compa rison of RP/IEX BimodalMixed-Mode Columns......Page 74
3.5.1 Pharmaceutical Active Ingredient s and Counterions......Page 78
3.5.2 Melamine and Cyanuric Acid......Page 80
3.5.3 Buffer Salts for Biopharmaceutical Applications......Page 84
3.5.4 Determination of Ethanol Consumption Markers......Page 86
3.6 Concluding Remarks......Page 87
Acknowledgments......Page 88
References......Page 89
4.1 Introduction......Page 92
4.2 Polyphenolic Compounds......Page 93
4.3 Chromatography Challenges for Separation of Various PAs......Page 94
4.4 HILIC Conditions for Separation of PAs......Page 95
4.6 Retention Behavior of Oligomeric PA S tandards in HILI C......Page 96
4.7 Retention Mechanism of Oligomeric PAs in HILI C......Page 99
4.8 HILIC Separation of Other Polyphenolic Compounds......Page 101
References......Page 103
5.1 Introduction......Page 104
5.2.1 HILIC with Conventional Detectors......Page 105
5.2.2 HILIC Coupled to Mass Spectrometry......Page 110
5.3 Application of Hydrophilic Interaction Chromatography to the Analysis of Safety- Related Compounds in Foods......Page 111
References......Page 119
6.1 Introduction......Page 120
6.2 Paralytic Shellfish Poisoning Toxins......Page 123
6.2.1 HILIC -MS Determination of PSP Toxins......Page 124
6.2.2 Application to Plankton and Shellfish Samples......Page 135
6.3.1 HILIC -MS D ete rminat ion of DA......Page 137
6.3.2 Application to Shellfish Samples......Page 139
6.4.1 HILIC -MS Determination of Assorted Cyanobacterial Toxins......Page 141
6.4.2 Applications to Cyanobacterial Samples......Page 143
6.5 Conclusions......Page 145
References......Page 146
Contents......Page 148
7.2.1 Generalities......Page 149
7.2.2 Paralytic Shellfish Poisoning Toxins......Page 150
7.2.3 Tetrodotoxin and Analogs......Page 155
7.2.5 Concluding Remarks......Page 157
7.3.1 Estrogens......Page 158
7.3.2 Cytostatic Drugs......Page 161
7.3.4 Miscellaneous Pharmaceuticals......Page 162
7.3.5 Drugs of Abuse......Page 164
7.4 Pesticides......Page 165
7.4.2 Phenylurea Herbicides......Page 166
7.4.3 Quaternary Ammonium Salt Herbicides......Page 167
7.5.2 Oligosaccharides......Page 168
References......Page 169
Contents......Page 172
8.1.2 Antimicrobials in the Environment......Page 173
8.1.4 Analysis of Spectinomycin and Lincomycin......Page 175
8.1.5 Spectinomycin......Page 176
8.1.7 Objective......Page 177
8.2.3.1.1 Liquid Swine Manure......Page 178
8.2.4.1.1 Manure Liquid Component......Page 179
8.2.4.2.2 Manure Solids Component......Page 180
8.2.6.2 Mass Spectrometer......Page 181
8.3.2.1 Liquid Manure......Page 182
8.3.3 Mass Spectrometry......Page 183
8.3.4 Chromatography......Page 185
8.3.6 Application of Method to Analysis of Environmental Matrices......Page 188
References......Page 189
Contents......Page 192
9.1 Characteristics of Clinical Samples and Clinical Analysis......Page 193
9.2.2 Biomarker Profiling......Page 194
9.2.3.1.2 Free Metanephrines......Page 195
9.2.3.1.4 Methylmalonic Acid......Page 196
9.2.3.1.6 Ornithine......Page 197
9.2.3.1.8 Tobacco-Specific Nitrosamine Metabolites......Page 199
9.2.3.2.2 1,5-Anhydroglucitol......Page 201
9.2.3.2.3 Arginine, Synthetic Dimethylarginine, and AsymmetricDimethylarginine......Page 202
9.2.3.2.4 Cocaine and Metabolites......Page 203
9.2.3.2.6 Organophosphorus Nerve Agent Metabolites......Page 204
9.2.3.3.1 3-Nitrotyrosine, Tyrosine, Hydroxyproline, and Proline......Page 205
References......Page 206
10.1 Introduction......Page 218
10.2 Arginine and Its Dimethyl Derivatives......Page 219
10.3 MS Setup......Page 220
10.4.2 Effect of ACN Percentage on HILIC and Comparison between Organic-Rich and Water-Rich Mobile Phaseon Silica Column Chromatography......Page 222
10.4.3 Effect of TFA Percentage on the HILIC Method......Page 226
10.4.4 Effect of Column Temperature on the HILIC Method......Page 227
10.5 Plasma Method......Page 229
10.7 Method Development for the Analysis of CSF......Page 234
References......Page 237
11.1 Introduction......Page 240
11.2 Ionic Functional Groups in HILIC Separation......Page 242
11.2.1 Effect of Stationary Phase Composition......Page 243
11.2.2 Effect of Buffer Concentration Ionic Strength......Page 248
11.2.3 Effect of Column Temperature......Page 254
11.3.1 Effect of Mobile Phase Composition......Page 259
11.3.2 Effect of Column Temperature......Page 267
References......Page 271
Contents......Page 273
12.1 Introduction......Page 274
12.2 Trace Analysis of Genotoxic Impurities......Page 275
12.2.1 Alkyl Sulfonates......Page 277
12.2.2 Alkyl Halides......Page 281
12.3.2 3S-3-Morpholine methanol......Page 287
12.3.4 Organic Acids......Page 289
12.4.1 5-Fluorouracil in 5-Fluorocytosine......Page 290
12.4.2 Guanine in Acyclovir......Page 291
12.4.3 Epirubicin......Page 292
12.4.4 Chiral Compounds......Page 293
12.4.5 Carbamates......Page 294
12.4.6 Sodium Cromoglicate......Page 296
12.5 Counterion A nalysis......Page 297
12.6 Conclusions and Future Prospects......Page 299
References......Page 301
13.1.1 HILIC and HILIC Stationary Phases......Page 304
13.1.2 Overview of UPLC and HILIC -UPLC Applications......Page 306
13.2.1 Introduction......Page 308
13.2.2 Experimental......Page 309
13.2.3.1 Univariate Method Development......Page 310
13.2.3.2 Multivariate Method Optimization......Page 313
References......Page 317
14.1 Introduction......Page 321
14.2 Eff ect of Organic S olvent......Page 324
14.3 Effect of Acetonitrile Content on Retention with Different Stationary Phases......Page 328
14.4 Effect of pH......Page 333
14.5 Effect of Buffer Concentration with Various Stationary Phases......Page 338
14.6 Temperature Effect with Various Stationary Phases......Page 344
14.7 Application Results and Method Validation......Page 350
References......Page 353
15.1 Introduction......Page 356
15.2.1.1 HILIC-Column Screening......Page 358
15.2.1.2 Mobile-Phase Components......Page 359
15.2.1.2.1 Mobile-Phase Strength......Page 361
15.2.1.2.2 Mobile-Phase pH......Page 364
15.2.1.2.3 Ionic Strength of Mobile Phase......Page 365
15.2.1.3 Column Temperature......Page 367
15.2.2 Method Validation......Page 369
15.3.1.1 Alcohol as a Weak Eluent......Page 371
15.3.1.2 Combined ZIC and HILIC Modes......Page 372
15.3.1.3 Type of Acid Additive......Page 373
15.3.1.4 Type of Buffer and Ionic Strength......Page 376
15.3.2 Method Validation......Page 379
References......Page 380
16.1 Introduction......Page 384
16.2 Analysis of Pharmaceutical Ingredients......Page 385
16.2.4 SCG in Ophthalmic Solution......Page 386
16.3 Retention Mechanism......Page 388
16.3.1.1 Choice of Organic Solvent......Page 389
16.3.1.2 Use of Alternate Solvent......Page 390
16.3.2 Mobile-Phase pH and Ion Exchange......Page 391
16.3.3 Ionic Strength......Page 397
16.3.4 Stationary Phase......Page 398
16.3.5 Diluent and Injection Volume......Page 402
16.3.6 Validation of Methods......Page 403
16.4 Advantages......Page 404
References......Page 408
17.1 Introduction......Page 411
17.2 Polar Stationary Phases for HILI C......Page 412
17.3 Selectivity of Various Polar Stationary Phases in HILIC......Page 416
17.4 Retentivity of Various Polar Stationary Phases in HILIC......Page 423
17.5 Factors Affecting Retention and Selectivity in HILIC......Page 425
17.6 Separation of Positional Isomers in HILI C......Page 432
17.7 Conclusions......Page 433
References......Page 434
Contents......Page 436
18.2 Application of HILI C- MS / MS in the Field of Pharmacokinetics? Bioequivalence Studies......Page 437
18.4 Pharmacokinetics S tudies of Donepezil, Loratadine, and Cetirizine......Page 438
18.6 Pharmacokinetic Study of the Peptide Drug Taspoglutide......Page 443
18.7 HILIC- ESI - MS / MS Method for the Quantitation of Polar Metabolites of Acrylamide in Human Urine......Page 445
18.8 HILIC- MS / MS Technique f or Sensitive Monitoring of the Changes of Urinary E strogen Conjugates......Page 446
18.9 Combination of HILIC- MS and RPLC- MS for Profiling Polar Urine Metabolites......Page 447
References......Page 450
19.1 Introduction......Page 453
19.2.1 Chemicals and Materials......Page 455
19.2.3 Physiochemical Parameters......Page 459
19.3.1 Optimal pH......Page 460
19.3.3 Gradient Method Development......Page 464
19.3.5 Separation Results......Page 465
19.3.6 Method Validation......Page 469
Acknowledgments......Page 472
References......Page 473
20.1 Introduction......Page 476
20.2 Protein Modifications: Glycosylation......Page 478
20.3 Troubles in Glycoproteome Analysis......Page 479
20.4 Enrichment Methods for Glycoproteome......Page 480
20.5 HILIC: Mechanism and Material......Page 481
20.6 HILIC: From Glycomics to Glycoproteomics......Page 484
20.7 Glycoproteomics by HILIC and Mass Spectrometry......Page 485
20.8 Application to Biomarker Discovery......Page 489
References......Page 492
Contents......Page 497
21.1.2 Techniques for Separation and Detection of Carbohydrates......Page 498
21.1.3 HILIC in the Separation of Carbohydrates......Page 500
21.2.1 Use of Different Stationary Phases......Page 504
21.2.2 Mobile-Phase Composition......Page 505
21.2.3 Temperature and Other Variables......Page 511
21.2.4 Sample Preparation Strategy......Page 514
21.2.5 Detection of Carbohydrates......Page 515
21.2.6 Short Outline for the Development of an HILIC Method......Page 517
21.3.1 HILIC Separation of Mono-, Di-, and Oligosaccharidesby Cyclodextrin Columns in Combinat ion with UV an d RI Detection......Page 518
21.3.2 HILIC Separation by an Amide-80 Columnand MS Analysis of Carbohydrates from Plants......Page 519
21.3.3 HILIC Separation by a ZIC -HILIC Column and MS Analysisof Tryptic Glycopeptides from Human Immunoglobulin......Page 520
21.3.5 Separation of Glucosinolate s by a ZIC -HILIC Column and Detection by Absorbance......Page 521
21.3.6 Separation of GAGs by an Amide-80 Column Combined with MS Analysis......Page 523
References......Page 526
Contents......Page 529
22.1.1 Importance of Glycosylat ion in Biological Systems and How Variation Can Lead to Disease......Page 530
22.1.2 Types of Glycosylation and Glycan Patterns......Page 531
22.1.3.2 MALDI -MS......Page 533
22.2.1 Glycoprote in Enrichment from Complex Solutions......Page 534
22.2.1.1 Lectin Affinity Chromatography......Page 535
22.2.1.3 Other Separation Techniques......Page 536
22.2.2.1 Hydrophilic Interaction Liquid Chromatography......Page 537
22.2.2.3 Hydrazine Chemistry......Page 540
22.2.2.5 Others......Page 541
22.3 Examples of Glycoprotein Characterization Using HILIC......Page 542
22.3.2 Characterization of Glycoforms......Page 543
22.3.3 Characterization of Glycosylation Site Occupancy......Page 544
22.3.4 Full Characterization of Glycoproteins......Page 546
References......Page 548
Contents......Page 557
23.2 Background......Page 558
23.3.1 HILIC SPE for Sample Prepa rat ion of Glycan s an d Glycopept ides......Page 560
23.3.1.1 Selective Enrichment of Glycopeptidesfrom Purified/Semi-Purified Glycoprotein......Page 561
23.3.1.2 Enrichment and Desalting of Released Glycans......Page 563
23.3.1.4 Enrichment of Glycopeptides from Complex Mixture Using HILIC SPE......Page 565
23.3.2.1 HILIC Separation of Glycans with Off-Line MS Detection......Page 569
23.3.2.2 HILIC Separation of Glycopeptides with Off-Line MS Detection......Page 570
23.3.2.3 Online HILI C-MS of Glycans......Page 571
23.3.2.4 Online HILI C-MS of Glycopeptides......Page 572
23.4.1.2 Strong Cation Exchange......Page 573
23.4.3.1 Early Applications of HILI C in Phosphoprotein/Peptide Analysis......Page 574
23.4.3.2 Application in Phosphoproteomics......Page 575
23.4.4 Electrostatic Repulsion Hydrophilic Interaction Chromatography......Page 576
23.4.5 Multiphosphopeptide Enrichment Prior to HILIC Fractionation......Page 577
References......Page 578