CONTENTS
Acknowledgments = ⅴ
Preface = ⅶ
1. Introduction to Mass Spectrometry／Mass Spectrometry = 1
1.1. History of mass spectrometry／mass spectrometry = 1
1.2. Concepts and principles = 3
1.3. Nomenclature = 12
2. MS／MS Instrumentation = 15
2.1. Introduction = 15
2.2. Principles of charged-particle analysis = 16
2.2.1. Electric sectors = 17
2.2.2. Magnetic sectors = 17
2.2.3. Quadrupole mass filters = 18
2.2.4. Time-of-flight analysis = 19
2.2.5. The Wien filter = 19
2.2.6. Fourier transform-ion cyclotron resonance = 20
2.2.7. Ion trap mass spectrometers = 21
2.3. Sector-based MS／MS instruments = 22
2.3.1. One-sector instruments = 22
2.3.2. Two-sector MS／MS instruments = 23
2.3.3. Three- and four-sector MS／MS instruments = 30
2.4. Quadrupole instruments = 34
2.5. Hybrid instruments = 36
2.6. MS／MS with ion-trapping techniques = 45
2.6.1. MS／MS with an FT-ICR = 45
2.6.2. MS／MS with an ITMS = 48
2.7. Reaction regions = 50
2.7.1. Kiloelectron-volt ion kinetic energy reaction regions = 50
2.7.2. Electron-volt ion energy reaction regions = 51
3. Reactions in MS／MS = 53
3.1. Introduction = 53
3.2. Unimolecular dissociation = 54
3.3. Activation reactions = 63
3.3.1. Collisional activation = 64
3.3.1.1. Kinematics = 66
3.3.1.2. Dynamics = 70
3.3.1.3. Kiloelectron- volt collision energy collisional activation = 75
3.3.1.4. Eicctron-volt collision energy collisional activation = 78
3.3.1.5. Target gas effects = 83
3.3.2. Photodissociation = 86
3.3.3. Electron excitation = 90
3.3.4. Surface-induced dissociation = 93
3.4. Reactive collisions = 95
3.5. Charge permutation reactions = 99
3.5.1. Charge exchange reactions = 99
3.5.1.1. $$m_p$$ ＋ N →$$m_p$$ ＋ N = 99
3.5.1.2. $$m_p$$ ＋ N →$$m_p$$ ＋ N = 100
3.5.1.3. $$m^2_p$$ ＋ N →$$m_p$$ ＋ N = 101
3.5.2. Collisional ionization reactions = 102
3.5.2.1. $$m_p$$ ＋ N →$$m_p$$ ＋ N ＋ 2e = 102
3.5.2.2. $$m_p$$ ＋ N →$$m^2_p$$ ＋ N ＋ e = 103
3.5.2.3. $$m_p$$ ＋ N →$$m_p$$ ＋ N ＋ e = 105
4. Applications of MS／MS to Fundamental Studies = 107
4.1. Introduction = 107
4.2. Ion structures = 107
4.2.1 Unimolecular chemistry = 108
4.2.1.1. Metastable ions = 110
4.2.1.2. Activated ions = 112
4.2.2. Bimolecular chemistry = 120
4.2.3. Neutral structures = 122
4.3. Reaction mechanisms = 123
4.3.1. Unimolecular reactions in the ion source = 124
4.3.2. Unimolecular reactions in reaction regions = 126
4.3.3. Bimolecular reactions in the ion source = 131
4.3.4. Bimolecular reactions in a reaction region = 132
4.4. Thermochemistry = 137
4.4.1. Energy gain／loss measurements = 137
4.4.2. Kinetic energy release measurements = 144
4.4.3. Relative product ion abundances = 145
4.4.3.1. Thermochemical information from ion-bound dimers = 145
4.4.3.2. Ion internal energies from ion abundances = 149
5. Characteristics of MS／MS for Analytical Applications = 153
5.1. Sample considerations = 153
5.1.1. Sample collection = 153
5.1.2. Sample contamination = 155
5.1.3. Sample derivatization = 155
5.2. Choice of ionization method = 157
5.2.1. Review of ionization methods = 157
5.2.2. Analytical requirements for sample ionization = 159
5.2.2.1. Molecular and ionic structural correspondence = 159
5.2.2.2. Ion flux = 160
5.2.3. Matrix effects = 161
5.3. Interpretation of MS／MS spectra = 162
5.3.1. High-energy MS／MS spectra = 163
5.3.2. Low-energy MS／MS spectra = 167
5.3.3. Automated systems = 169
6. Analytical Applications = 173
6.1. Environmental applications = 173
6.1.1. Priority pollutant analysis = 174
6.1.2. Polyhalogenated compounds = 175
6.1.3. Atmospheric pollutants = 178
6.1.4. Water pollutants = 179
6.1.5. Indoor air pollution = 179
6.2. Natural products applications = 180
6.2.1. Alkaloids, lipids, and other naturally occurring compounds = 180
6.2.2. Toxic natural compounds = 187
6.3. Industrial products applications = 191
6.3.1. Dyes = 192
6.3.2. Surfactants = 193
6.3.3. Polymers = 194
6.3.4. Rubber and rubber additives = 198
6.3.5. Agricultural products = 199
6.4. Foods and flavors applications = 199
6.4.1. Food components = 201
6.4.2. Food additives = 205
6.5. Forensic chemistry applications = 206
6.6. Petroleum and petroleum products applications = 209
6.6.1. Geochemical applications = 210
6.6.2. Fuel characterization = 212
6.6.3. Dating techniques with accelerator mass spectrometry = 216
6.7. Bioorganic applications = 216
6.7.1. Biological compound classes = 217
6.7.1.1. Carbohydrates and saccharides = 217
6.7.1.2. Nucleosides and nucleotides = 224
6.7.1.3. Fatty acids and lipids = 232
6.7.1.4. Steroids = 235
6.7.1.5. Bioamines = 246
6.7.1.6. Peptides = 248
6.8. Pharmaceutical applications = 265
6.8.1. Drug assays and drug structures = 266
6.8.2. Drug residues = 270
6.8.3. Drug metabolites = 273
6.8.4. Diagnosis and metabolic profiling = 276
6.9. Applications to continuous flow samples and processes = 277
7. Conclusions and Outlook = 279
7.1. Instrumentation in MS／MS = 279
7.2. Outlook for advanced applications = 280
7.3. Interpretation of MS／MS data = 282
7.4. Conclusions = 283
References = 285
Appendix A: MS／MS Scan Modes on Various Instrument Configurations = 311
Appendix B: Frequently Used Symbols and Acronyms = 317
Index = 321
