Mass Spectrometry Basics

By: Christopher G. Herbert, Robert A.W. Johnstone

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Hardcover | 26 June 2002 | Edition Number 1

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498 Pages

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25.4 x 17.78 x 2.69

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Mass Spectrometry Basics provides authoritative yet plain-spoken explanations of the basic concepts of this powerful analytical method without elaborate mathematical derivations. The authors describe processes, applications, and the underlying science in a concise manner supported by figures and graphics to further comprehension. The text provides practical approaches to interpreting mass spectral data and step-by-step guides for identifying chemically relevant compounds. Additionally, the authors have included an extensive reference section and a quick guide to each chapter that offers immediate access to key information.

This unique reference makes some of the esoteric aspects of this important area of analysis more readily comprehensible to those who deal with analytical instruments but who have not been trained in mass spectrometry. It also serves as a refresher for practicing mass spectroscopists by clarifying principles to afford a better appreciation and application of this technology.

Industry Reviews

"This book is intended ... as a brief primer on the many flavors and applications of MS technology. As such, the novice will walk away with a taste of MS while the seasoned pioneer will see this book as a quick reference. ... [T]he book sets the reader up to read ... more complex books down the road. And each chapter is spiced with figures, tables, and schematics that help the reader understand how this technology comes together."
- Today's Chemist at Work

"...can be used by all categories of readership...The book is developmental in nature - beginning with basics of the process and proceeding stepwise to more detailed analyses of each aspect of the method...Highly recommended"
L. Andersson, Big Bend Community College, in CHOICE Magazine.

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Non-Fiction Reference, Information & Interdisciplinary Subjects Encyclopaedias & Reference Works Reference Works Science Chemistry Analytical Chemistry Spectrum Analysis Engineering & Technology Industrial Chemistry & Manufacturing Technologies Industrial Chemistry Biology, Life Sciences

Life Sciences in General

Chemical Ionization (CI)	p. 1
The Ionization Process	p. 1
Example of the Chemical Ionization Process	p. 1
Other Reagent Gases	p. 2
Other Ionization Routes	p. 3
Uses of CI	p. 4
Use of CI/EI in Tandem in GC/MS	p. 4
Negative Ions	p. 5
Conclusion	p. 5
Laser Desorption Ionization (LDI)	p. 7
The Ionization Process	p. 7
Other Considerations on Laser Desorption Ionization	p. 9
Use of a Matrix	p. 9
Types of Laser	p. 10
Secondary Ionization	p. 10
Uses of Lasers	p. 11
Conclusion	p. 12
Electron Ionization (EI)	p. 13
The Ionization Process	p. 13
Mass-To-Charge Ratio (m/z)	p. 13
The Mass Spectrum	p. 14
The Ion Source	p. 14
Isotopes	p. 16
Conclusion	p. 16
Fast-Atom Bombardment (FAB) and Liquid-Phase Secondary Ion Mass Spectrometry (LSIMS) Ionization	p. 17
Introduction	p. 17
Atom or Ion Beams	p. 18
The Ionization Process	p. 18
Properties of the Solvent (Matrix)	p. 20
The Mass Spectrum	p. 21
Conclusion	p. 22
Field Ionization (FI) and Field Desorption (FD)	p. 23
Introduction	p. 23
Field Ionization	p. 23
Design of the Needle Tip Electrode	p. 24
Practical Considerations of Field Ionization/Field Desorption	p. 25
Types of Compounds Examined by FI/FD	p. 27
Conclusion	p. 27
Coronas, Plasmas, and Arcs	p. 29
Background	p. 29
Electric Discharges in a Gas	p. 30
Light and Dark Regions in the Discharge	p. 32
Electric-Field Gradients across the Glow Discharge	p. 35
Self-Sustaining Discharge	p. 36
Sputtering	p. 36
Effect of Electrode Separation on Discharge	p. 37
Arcs	p. 37
Effect of Gas Pressure on Discharge	p. 38
Effect of Gas Flow on Discharge	p. 38
Effect of Electrode Shapes on Discharge	p. 38
Effect of Voltage Changes on Glow Discharge Characteristics	p. 39
Overall Process	p. 43
Conclusion	p. 43
Thermal Ionization (TI), Surface Emission of Ions	p. 45
Introduction	p. 45
High Filament Temperatures	p. 18
Thermochemistry of surface emission	p. 47
Changing the Work Function (Activators)	p. 49
Amount of Sample	p. 51
Measurement of Ratios of Isotopic Abundances	p. 51
Conclusion	p. 53
Electrospray Ionization (ESI)	p. 55
Introduction	p. 55
Differential Solvent Removal	p. 56
Multicharged ions	p. 57
Uses of Electrospray	p. 58
General Comments	p. 59
Conclusion	p. 60
Atmospheric-Pressure Ionization (API)	p. 61
Background	p. 61
The Ionization Process	p. 61
Drying Gas	p. 62
The Number of Ions	p. 63
Conclusion	p. 63
Z-Spray Combined Inlet/Ion Source	p. 65
Introduction	p. 65
The Initial Spray	p. 65
Trajectories of Ions and Neutrals	p. 67
Advantages	p. 68
Conclusion	p. 69
Thermospray and Plasmaspray Interfaces	p. 71
Introduction	p. 71
Differential Solvent Removal	p. 72
Ion Yield	p. 73
Nature of the Ions Produced	p. 73
Uses of Plasmaspray and Electrospray	p. 74
General Comments	p. 75
Conclusion	p. 75
Particle-Beam Interface	p. 77
Background	p. 77
The Nebulizer	p. 77
The Evacuation Chamber	p. 77
The First Skimmer	p. 78
The Second Skimmer	p. 78
The Ion Source	p. 79
Ionization	p. 79
Efficiency	p. 79
Similarity to Other Interfaces	p. 79
Conclusion	p. 80
Dynamic Fast-Atom Bombardment and Liquid-Phase Secondary Ion Mass Spectrometry (FAB/LSIMS) Interface	p. 81
Introduction	p. 81
Atom or Ion Beams	p. 82
Properties of the Solvent (Matrix Material)	p. 82
Dynamic-FAB/LSIMS Interface	p. 83
Types of Ions Produced	p. 86
Conclusion	p. 86
Plasma Torches	p. 87
Introduction	p. 87
Construction of the Plasma Torch	p. 88
Plasma Flame	p. 89
Temperature of the Plasma	p. 91
Processes Occurring in the Plasma after Introduction of a Sample	p. 92
Cold Plasma Conditions and the Plasma Cage	p. 94
The Interface	p. 95
Conclusion	p. 95
Sample Inlets for Plasma Torches, Part A: Gases	p. 97
Introduction	p. 97
Problems of Sample Introduction	p. 97
Introduction of Gases	p. 98
Conclusion	p. 102
Sample Inlets for Plasma Torches, Part B: Liquid Inlets	p. 103
Introduction	p. 103
Problems of Sample Introduction	p. 103
Liquid Inlets	p. 104
Direct Insertion Methods (Direct Solids Insertion, DSI)	p. 105
Electrothermal Heating Methods (Electrothermal Vaporization, ETV)	p. 106
Nebulizer Methods	p. 106
Desolvation Chambers	p. 107
Conclusion	p. 108
Sample Inlets for Plasma Torches, Part C: Solid Inlets	p. 109
Introduction	p. 109
Problems of Sample Introduction	p. 109
Introduction of Solids	p. 110
Conclusion	p. 116
Lasers and Other Light Sources	p. 117
Introduction	p. 117
Some Characteristics of Light as a Waveform	p. 120
Nonlaser Light Sources	p. 122
Laser Light Sources	p. 123
Lasers in Mass Spectrometry	p. 134
Conclusion	p. 136
Nebulizers	p. 137
Background	p. 137
The Nature of an Aerosol	p. 137
General Principles of Aerosol Formation	p. 138
Pneumatic Nebulizers (PN)	p. 139
Ultrasonic Nebulizers (USN)	p. 147
Thermospray Nebulizers (TN)	p. 149
Electrospray Nebulization (EN)	p. 150
Spray and Desolvation Chambers	p. 152
Conclusion	p. 152
Hybrid Orthogonal Time-of-Flight (oa-TOF) Instruments	p. 153
Introduction	p. 153
Q/TOF	p. 153
LC/TOF	p. 154
AutoSpec-TOF	p. 154
Conclusion	p. 154
Hybrid Magnetic-Sector Time-of-Flight (Sector/TOF) Instruments	p. 157
Introduction	p. 157
AutoSpec-TOF Ion Optics	p. 158
Magnetic/Electric-Sector Section	p. 158
Time-of-Flight Section	p. 159
Operation of the Combined Magnetic and TOF Sectors as a Hybrid Instrument	p. 160
Other Advantages of the Hybrid	p. 161
Conclusion	p. 161
Hybrid Hexapole Time-of-Flight (Hexapole/TOF) Instruments	p. 163
Introduction	p. 163
Inlet Systems	p. 163
Hexapole Bridge	p. 164
Time-of-Flight Analyzer	p. 165
Operation of the Hybrid	p. 166
Some Advantages of the Hybrid	p. 167
Conclusion	p. 167
Hybrid Quadrupole Time-of-Flight (Q/TOF) Instruments	p. 169
Introduction	p. 169
The Separate Quadrupole and Time-of-Flight Analyzers	p. 169
Operation of the Hybrid	p. 172
Some Advantages of the Hybrid	p. 172
Conclusion	p. 173
Ion Optics of Magnetic/Electric-Sector Mass Spectrometers	p. 175
Introduction	p. 175
Mass Analysis of Ions	p. 175
Conclusion	p. 181
Quadrupole Ion Optics	p. 183
Background	p. 183
Equations of Motion of Ions	p. 183
Comparison of Quadrupole and Magnetic Sector Instruments	p. 185
The Choice of Quadrupole or Magnetic-Sector Instruments	p. 186
Conclusion	p. 186
More Details of Equations of Motion	p. 186
Time-of-Flight (TOF) Ion Optics	p. 189
Background	p. 189
Equations of Motion of Ions	p. 189
Resolution	p. 190
Reflectron	p. 191
Comparison with Other Mass Spectrometers	p. 191
Conclusion	p. 193
Orthogonal Time-of-Flight (oa-TOF) Ion Optics	p. 195
Introduction	p. 195
The Physical Basis of Orthogonal TOF	p. 196
Pulsed Main Beams of Ions	p. 196
Rate of Application of the Pulsed-Field Gradient	p. 197
Microchannel Plate Ion Collector	p. 197
Resolution by m/z Value	p. 198
MS/MS Operation	p. 198
Advantages of Orthogonal TOF Arrangements	p. 199
Conclusion	p. 199
Point Ion Collectors (Detectors)	p. 201
Introduction	p. 201
Types of Point Ion Collector	p. 201
Conclusion	p. 204
Array Collectors (Detectors)	p. 205
Introduction	p. 205
Array Detection	p. 206
An Element of the Array	p. 206
Separation of Array Elements (Ion Mass Range)	p. 207
Dynamic Range (Ion Abundance)	p. 209
Uses of Array Collectors	p. 209
Conclusion	p. 210
Comparison of Multipoint Collectors (Detectors) of Ions: Arrays and Microchannel Plates	p. 211
Introduction	p. 211
Arrays and Microchannel Plates	p. 213
The Elements of Array and Microchannel Plates	p. 214
Array Elements (Ion Mass Range)	p. 215
Microchannel Elements (Ion Mass Range)	p. 215
Uses of Array and Microchannel Collectors	p. 216
Conclusion	p. 217
Time-to-Digital Converters (TDC)	p. 219
Background	p. 219
Measurement of m/z Ratios by Time-of-Flight Instruments	p. 219
Multichannel (Microchannel) Plate Array	p. 220
Timing of Electrical Pulses Resulting from Ion Arrivals at the Microchannel Plate Collector	p. 221
Ion Abundances and Dead Time	p. 223
Conclusion	p. 224
Origin and Uses of Metastable Ions	p. 225
Introduction	p. 225
Field Free Zones and the Formation of Metastable Ions	p. 226
Abundances of Metastable Ions	p. 227
Disadvantage of Low Abundance of Metastable Ions	p. 228
Enhanced (Induced) Fragmentation	p. 228
Conclusion	p. 229
Linked Scanning and Metastable Ions in Quadrupole Mass Spectrometry	p. 231
Introduction	p. 231
Normal and Metastable Ions	p. 231
How Quadrupoles Can Be Used to Examine Metastable Ions	p. 233
Linked Scanning with Triple Quadrupole Analyzers	p. 233
Use of Metastable Ion and CID Data	p. 235
Conclusion	p. 235
Linked Scanning and Metastable Ions in Magnetic-Sector Mass Spectrometry	p. 237
Introduction	p. 237
Electric/Magnetic-sector Geometry	p. 238
Metastable Ions Decomposing in the First Field-Free Region	p. 238
Metastable Ions Decomposing in the Second Field-Free Region	p. 239
Metastable Ions Decomposing in the Third Field-Free Region	p. 240
Linked Scanning of V, E, and B Fields	p. 240
E[superscript 2]/V Scan	p. 240
B/E Scan	p. 241
B[superscript 2]/E Scan	p. 241
(B/E)(1 - E)_ Scan	p. 242
Application of Linked Scanning	p. 242
Linked Scanning, Ion Traps, and Hybrid Mass Spectrometers	p. 243
Conclusion	p. 244
Gas Chromatography (GC) and Liquid Chromatography (LC)	p. 245
Introduction	p. 245
Principles of Gas and Liquid Chromatography	p. 245
Requirements for Chromatographic Apparatus	p. 246
The Chromatographic Process	p. 248
Injectors	p. 250
Detectors	p. 250
Uses of GC and LC	p. 251
Conclusion	p. 252
Gas Chromatography/Mass Spectrometry (GC/MS)	p. 253
Introduction	p. 253
Connection between GC and MS	p. 254
Recording Mass Spectra	p. 255
Manipulation of Scan Data	p. 257
Conclusion	p. 260
Liquid Chromatography/Mass Spectrometry (LC/MS)	p. 261
Introduction	p. 261
Connection Between LC and MS	p. 262
Recording Mass Spectra	p. 264
Manipulation of Scan Data	p. 265
Conclusion	p. 268
High-Resolution, Accurate Mass Measurement: Elemental Compositions	p. 269
Introduction	p. 269
Atomic and Molecular Mass: Fragment Ion Mass	p. 269
The Value of Accurate Mass Measurement	p. 271
Resolution of Mass Spectrometers	p. 271
Measurement of Accurate Mass	p. 272
Conclusion	p. 274
Choice of Mass Spectrometer	p. 275
Introduction	p. 275
Objectives in Buying a Mass Spectrometer	p. 275
Types of Sample	p. 276
Complexity of Sample	p. 276
Sample Volatility, Polarity, and Thermal Stability	p. 278
Mass Analyzers	p. 280
Ionization Methods	p. 282
Overall View of Choices	p. 285
Conclusion	p. 285
Analysis of Peptides and Proteins by Mass Spectrometry	p. 287
Introduction	p. 287
Fast-Atom Bombardment (FAB)	p. 287
Dynamic FAB	p. 288
Mass Spectrometry--Mass Spectrometry (MS/MS)	p. 288
Other Ion Sources	p. 290
Conclusion	p. 294
Environmental Protection Agency Protocols	p. 295
Introduction	p. 295
Environmental Laws	p. 295
The Contract Laboratory Program	p. 296
Protocols	p. 296
Sample Analysis by GC/MS	p. 296
Conclusion	p. 301
Computers and Transputers in Mass Spectrometers, Part A	p. 303
Introduction	p. 303
Multibase Arithmetic	p. 303
Binary Arithmetic	p. 304
Electronic Switching and Binary Code	p. 306
Registers	p. 306
Other Registers	p. 307
Bits and Bytes	p. 308
Languages	p. 309
Computer Memory	p. 309
The Clock	p. 310
Conclusions	p. 310
Computers and Transputers in Mass Spectrometers, Part B	p. 311
Introduction	p. 311
Basic Speed Differential between Parallel and Serial Modes	p. 311
Occam	p. 314
Reduced Instruction Set for Computing (RISC)	p. 314
Conclusion	p. 315
Computers and Transputers in Mass Spectrometers, Part C	p. 317
Introduction	p. 317
Data Processing	p. 317
Instrument Control	p. 320
Manipulation of Mass Spectral Data	p. 322
Conclusion	p. 325
Introduction to Biotechnology	p. 327
Genetics	p. 327
Proteins	p. 330
Conclusion	p. 334
Isotopes and Mass Spectrometry	p. 335
Introduction	p. 335
Atomic Structure and the Elements	p. 335
Atomic Nucleus and Isotopes	p. 339
Isotope Ratios	p. 339
Conclusion	p. 341
Uses of Isotope Ratios	p. 343
Introduction	p. 343
Isotope Ratios in Routine Mass Spectrometry	p. 343
Examples of the Use of Accurate Isotope Ratios	p. 350
Conclusion	p. 352
Variations in Isotope Ratios	p. 353
Background	p. 353
Radioactive and Nonradioactive Isotopes	p. 354
Standards for Isotope Ratios	p. 354
Basic Facets of Measuring Isotope Ratios	p. 354
Causes of Variation in Isotope Ratios	p. 362
Instruments Used to Measure Accurate Isotope Ratios	p. 365
Examples of Isotope Ratio Measurements	p. 366
Plutonium Contamination in the Environment	p. 369
Conclusion	p. 369
Transmission of Ions through Inhomogeneous RF Fields	p. 371
Background	p. 371
Gas pressure and ion/molecule collisions	p. 372
Overall Effects of Ion/Molecule Collisions and the Use of Ion Transmission Guides	p. 377
Inhomogeneous RF Fields Applied to Rod Assemblies	p. 378
Conclusion	p. 382
Collection of Summaries	p. 383
Glossary of Mass Spectrometry Definitions and Terms	p. 429
Books on Mass Spectrometry and Related Topics	p. 449
Regular Publications in Mass Spectrometry	p. 453
Publications Containing Occasional Papers Related to Mass Spectrometry	p. 455
Index	p. 457
Table of Contents provided by Syndetics. All Rights Reserved.

Mass Spectrometry Basics

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