Preface ........................................................ xi
List of Contributors ......................................... xiii
1 Quality Assurance, Quality Control and Method
Validation in Chromatographic Applications ................. 1
Michele L. Merves and Bruce A. Goldberger
1.1 Introduction ............................................... 1
1.2 History .................................................... 1
1.3 Definition of Quality Assurance and Quality Control ........ 3
1.4 Professional Organizations ................................. 4
1.5 Internal Quality Assurance and Control ..................... 5
1.5.1 Standard operating procedure manual ................. 5
1.5.2 Method development .................................. 5
1.5.3 Method validation ................................... 6
1.5.4 Accuracy ............................................ 7
1.5.5 Precision ........................................... 7
1.5.6 Recovery ............................................ 7
1.5.7 Lower limits of detection (sensitivity) and
quantitation ........................................ 8
1.5.8 Range of linearity .................................. 8
1.5.9 Specificity ......................................... 9
1.5.10 Stability ........................................... 9
1.5.11 Carryover ........................................... 9
1.5.12 Ruggedness .......................................... 9
1.5.13 Selection of a reference standard .................. 10
1.5.14 Selection of an internal standard and standard
addition ........................................... 10
1.5.15 Selection of derivatization agent .................. 10
1.5.16 Selection of ions for selected-ion monitoring
or full-scan analysis .............................. 11
1.5.17 Chromatographic performance ........................ 11
1.5.18 Statistical evaluation of quality control .......... 11
1.6 External Quality Assurance ................................ 13
References ................................................ 13
2 Liquid Chromatographic-Mass Spectrometric Measurement of
Anabolic Steroids ......................................... 15
Don H. Catlin, Yu-Chen Chang, Borislav Starcevic and
Caroline K. Hatton
2.1 Introduction .............................................. 15
2.2 LC-MS Analysis of Synthetic Steroids or Animal Samples .... 16
2.3 LC-MS Analysis of Natural Androgens in Human Samples ...... 19
2.4 Conclusion ................................................ 29
References ................................................ 29
3 High-performance Liquid Chromatography in the Analysis
of Active Ingredients in Herbal Nutritional Supplements ... 33
Amitava Dasgupta
3.1 Introduction .............................................. 33
3.2 St John's Wort ............................................ 35
3.2.1 Drug interactions with St John's wort .............. 35
3.2.2 Measurement of active ingredients of St John's
wort using HPLC .................................... 36
3.2.3 Analysis of St John's wort extract with other
analytical techniques .............................. 38
3.2.4 Measurement of hypericin and hyperforin in human
plasma using HPLC .................................. 38
3.3 Herbal Supplements with Digoxin-like Immunoreactivity ..... 39
3.3.1 Use of HPLC for the determination of chan su,
danshen and ginsengs ............................... 40
3.4 Herbal Remedies and Abnormal Liver Function Tests ......... 41
3.4.1 Use of GC-MS and HPLC for the measurement of
active components .................................. 43
3.5 Ginkgo Biloba ............................................. 43
3.5.1 Analysis of components of ginkgo biloba by HPLC .... 44
3.6 Echinacea ................................................. 45
3.6.1 Analysis of active components of echinacea by
HPLC ............................................... 45
3.7 Valerian .................................................. 46
3.7.1 Analysis of components of valerian by HPLC ......... 46
3.8 Feverfew .................................................. 46
3.8.1 Analysis of parthenolide by HPLC ................... 47
3.9 Garlic .................................................... 47
3.9.1 Measurement of components of garlic by HPLC ........ 48
3.10 Ephedra (Ma Huang) and Related Drugs ...................... 48
3.10.1 Analysis of active components of ephedra-
containing products ................................ 49
3.11 Conclusions ............................................... 50
References ................................................ 50
4 Measurement of Plasma l-DOPA and ь-Tyrosine by High-
Performance Liquid Chromatography as a Tumor Marker in
Melanoma .................................................. 56
Thierry Le Bricon, Sabine Letellier, Konstantin
Stoitchkov and Jean-Pierre Garnier
4.1 Introduction .............................................. 56
4.2 Melanogenesis ............................................. 57
4.2.1 Overview of the pathway ............................ 57
4.2.2 Potential tumor markers ............................ 58
4.3 l-DOPA Alone .............................................. 59
4.3.1 Urine analysis ..................................... 59
4.3.2 Blood (plasma or serum) analysis ................... 59
4.4 L-DOPA/L-Tyrosine Ratio ................................... 60
4.4.1 Technical aspects .................................. 60
4.4.2 Clinical results ................................... 61
4.4.3 Future directions .................................. 63
4.5 Conclusion ................................................ 64
References ................................................ 65
5 Hypersensitive Measurement of Proteins by Capillary
Isoelectric Focusing and Liquid Chromatography-Mass
Spectrometry .............................................. 67
Feng Zhou and Murray Johnston
5.1 Introduction .............................................. 67
5.2 A Robust CIEF-RPLC Interface .............................. 69
5.3 First-Generation CIEF-RPLC-MS System for Protefns ......... 71
5.4 Second-Generation CIEF-RPLC-MS System ..................... 76
5.5 Future Improvements ....................................... 83
Acknowledgment ............................................ 83
References ................................................ 83
6 Chromatographic Measurement of Transferrin Glycoforms
for Detecting Alcohol Abuse and Congenital Disorders of
Glycosylation ............................................. 87
Anders Helander
6.1 Introduction .............................................. 87
6.2 Transferrin Microheterogeneity ............................ 88
6.3 Carbohydrate-deficient Transferrin (CDT) .................. 89
6.4 Congenital Disorders of Glycosylation (CDG) ............... 89
6.5 Analytical Methods for Transferrin Microheterogeneity ..... 90
6.6 Chromatographic Methods for CDT ........................... 91
6.6.1 HPLC conditions and potential interferences ........ 91
6.6.2 Chromatographic separation of transferrin
glycoforms ......................................... 92
6.6.3 Genetic transferrin variants and glycoform types ... 94
6.6.4 Sensitivity and reproducibility .................... 94
6.7 Chromatographic Methods for CDG ........................... 94
6.7.1 HPLC testing for CDG ............................... 95
6.7.2 LC-MS testing for CDG .............................. 95
6.8 Summary and Conclusions ................................... 96
References ................................................ 97
7 Chromatographic Measurements of Catecholamines and
Metanephrines ............................................ 101
Eric C.Y. Chan and Paul C.L. Ho
7.1 Background ............................................... 101
7.1.1 Total or individual assays ........................ 104
7.2 Analytical Measurements of Catecholamines and
Metanephrines ............................................ 105
7.3 Early Methods ............................................ 105
7.3.1 Catecholamines .................................... 105
7.3.2 Metanephrines ..................................... 106
7.4 Current Chromatographic Methods .......................... 106
7.4.1 Chemistry of catecholamines ....................... 106
7.4.2 Specimen preparation .............................. 107
7.4.3 Fluorescence detection ............................ 109
7.4.4 Electrochemical detection ......................... 110
7.4.5 Chemiluminescence detection ....................... 112
7.4.6 Mass spectrometry ................................. 115
7.5 Practical Considerations for the Stability of Urinary
Catecholamines and Metanephrines During Storage .......... 117
7.6 Future Developments ...................................... 118
Dedication ............................................... 119
References ............................................... 119
8 Chromatographic Measurement of Volatile Organic
Compounds (VOCs) ......................................... 127
Larry A. Broussard
8.1 Introduction ............................................. 127
8.2 General Considerations ................................... 127
8.3 Intended Use ............................................. 128
8.4 Volatility of Compounds .................................. 128
8.5 Sample Collection, Handling and Storage .................. 129
8.6 Headspace Gas Chromatographic Methods .................... 129
8.7 Columns and Detectors .................................... 130
8.8 Identification, Quantitation and Confirmation ............ 130
8.9 Ethanol and Other Volatile Alcohols ...................... 131
8.10 Inhalants and Screening for Multiple VOCs ................ 132
8.11 Interpretation ........................................... 134
8.12 Conclusion ............................................... 136
References ............................................... 136
9 Chromatographic Techniques for Measuring
Organophosphorus Pesticides .............................. 139
H. Wollersen and F. Musshoff
9.1 Introduction ............................................. 139
9.2 Organophosphorus Pesticides (OPs) ........................ 141
9.2.1 Mechanism of action ............................... 141
9.2.2 Intoxication ...................................... 141
9.2.3 Progression of intoxication and longer term
risks ............................................. 145
9.2.4 Therapy ........................................... 146
9.2.5 Analytical procedures ............................. 146
9.3 Conclusion ............................................... 163
References .................................................... 164
10 Chromatographic Analysis of Nerve Agents ................. 170
Jeri D. Ropero-Miller
10.1 Introduction ............................................. 170
10.2 Neuromuscular Blockers ................................... 170
10.2.1 Background and uses ............................... 170
10.2.2 Classification, mechanism and duration of action .. 171
10.2.3 Effects and toxicity .............................. 173
10.2.4 Analysis .......................................... 173
10.3 Paralytic Shellfish Poisoning: Saxitoxin ................. 185
10.3.1 Background ........................................ 185
10.3.2 Toxicity .......................................... 187
10.3.3 Analysis .......................................... 188
10.4 Summary ................................................. 191
References .................................................... 195
11 History and Pharmacology of γ-Hydroxybutyric Acid ........ 197
Laureen Marinetti
11.1 Introduction ............................................. 197
11.2 History of Illicit Use of GHB ............................ 198
11.3 Clinical Use of GHB in Humans ............................ 200
11.4 History of Illicit Use of GBL and 1,4BD .................. 200
11.5 Distribution and Pharmacokinetics of GHB, GBL and 1,4BD .. 202
11.6 GHB Interpretation Issues and Post-mortem Production ..... 204
11.7 Analysis for GHB, GBL and 1,4BD .......................... 208
References ............................................... 213
12 Liquid Chromatography with Inductively Coupled Plasma
Mass Spectrometric Detection for Element Speciation:
Clinical and Toxicological Applications .................. 217
Katarzyna Wrobel, Kazimierz Wrobel and Joseph A. Caruso
12.1 Introduction ............................................. 217
12.2 Liquid Chromatography with Inductively Coupled Plasma
Mass Spectrometric Detection ............................. 218
12.3 Analytical Applications of Clinical and Toxicological
Relevance ................................................ 219
12.3.1 Arsenic ........................................... 219
12.3.2 Iodine ............................................ 234
12.3.3 Mercury ........................................... 234
12.3.4 Platinum .......................................... 240
12.3.5 Selenium .......................................... 245
12.4 Conclusions and Future Trends ............................ 260
12.5 Abbreviations ............................................ 260
References .................................................... 262
13 Applications of Gas Chromatography-Mass Spectrometry to
the Determination of Toxic Metals ........................ 274
Suresh K. Aggarwal, Robert L. Fitzgerald and David
A. Herold
13.1 Introduction ............................................. 274
13.2 Instrumentation .......................................... 275
13.3 Experimental Procedure ................................... 276
13.3.1 Preparation of internal standard solutions ........ 276
13.3.2 Digestion of biological sample .................... 276
13.3.3 Preparation of metal chelate ...................... 277
13.4 GC-MS Studies ............................................ 278
13.4.1 Memory effect evaluation .......................... 278
13.4.2 Precision and accuracy in measuring isotope
ratios ............................................ 281
13.4.3 Results of concentration determination of toxic
metals in biological samples ...................... 283
13.5 Conclusions .............................................. 284
References .................................................... 284
Index ......................................................... 287
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