The second edition of this ACOL text, which was first published in 1987, continues to provide the analyst with an excellent introduction to mass spectrometry by the adoption of a practical approach in which the theoretical and operational aspects of this major analytical technique are combined. In the revised edition of this text, the author has expanded upon and reorganised the earlier material in order to bring it completely up to date. In addition to the basic theory of ion formation and behaviour, instrumentation and the interpretation of the spectra of simple organic compounds, this new edition reflects a number of the very important developments which have taken place in this field since the late 1980s. These include the burgeoning area of hyphenated mass spectral techniques, including gas chromatography-mass spectrometry (GC-MS), liquid chromatography-gas chromatography (LC-GS) and tandem mass spectrometry (MS-MS). Associated newer methods of interfacing, such as electrospray and ionspray, particle-beam and continuous flow coupling and atmospheric-pressure chemical ionisation are also covered. The current widespread use of computing techniques in structure elucidation is also considered, along with the important area of inorganic mass spectrometry for analysing surfaces, bulk solids and solutions. Analytical Chemistry By Open Learning This series provides a uniquely comprehensive and integrated coverage of analytical chemistry, covering basic concepts, classical methods, instrumental techniques and applications. The learning objectives of each text are clearly identified and the student's understanding of the material is constantly challenged by self-assessment questions with reinforcing or remedial responses. The overall objective of Analytical Chemistry by Open Learning is to enable the student to select and apply appropriate methods and techniques to solve analytical problems, and to interpret the results obtained. We are grateful to Dr Roger Taylor of the University of Sussex, UK for supplying the spectrum of fullerene used on the front cover.
Dies ist die zweite Ausgabe des ACOL-Titels ber Massenspektrometrie. Sie wurde auf den neuesten Stand gebracht, um die, die mit der Anwendung oder dem Studium der Massenspektroskopie beginnen, zeitgem an das Thema heranzuf hren. Der Autor deckt in den Kapiteln ber Ionenquellen und Verfahren der Ionisierung, Massenanalyse, Ionennachweis und Fragmentierungsmuster die Grundlagen des Themas ab, schlie t aber auch Kapitel ber Tandem-Techniken (Gas- und Fl ssigkeitschromatographie - Massenspektrometrie und Massenspektrometrie - Massenspektrometrie) und ber atomare Massenspektrometrie einschlie lich induktiv gekoppelter Plasma-Massenspektrometrie (ICPMS) ein. Wie bei allen B chern der ACOL-Reihe sind Fragen zur Selbst berpr fung und deren L sungen enthalten.
This thoroughly updated second edition of the ACOL text on Mass Spectrometry gives a modern approach to those beginning to use or study mass spectrometry. Self assessment questions and solutions are included. Fundamentals and modern instrumental techniques are also covered in this book.
Contents
Preface
Introduction
Principles
Diagram of a Mass Spectrometer
History
Ion Free Path
1 Ion Sources
1.1 Electron Ionization
1.2 Chemical Ionization
1.2.1 Proton transfer
1.2.2 Adduct formation
1.2.3 Charge-transfer chemical ionization
1.2.4 Reagent gas
1.2.5 Negative ion formation
1.2.6 Desorption chemical ionization (DCI)
1.3 Field Ionization
1.4 Fast Atom Bombardment and Liquid Secondary Ion Mass Spectrometry
1.5 Field Desorption
1.6 Plasma Desorption
1.7 Laser Desorption
1.8 Matrix-Assisted Laser Desorption Ionization
1.8.1 Principle of MALDI
1.8.2 Practical considerations
1.8.3 Fragmentations
1.8.4 Atmospheric pressure matrix-assisted laser desorption ionization
1.9 Thermospray
1.10 Atmospheric Pressure Ionization
1.11 Electrospray
1.11.1 Multiply charged ions
1.11.2 Electrochemistry and electric field as origins of multiply charged ions
1.11.3 Sensitivity to concentration
1.11.4 Limitation of ion current from the source by the electrochemical process
1.11.5 Practical considerations
1.12 Atmospheric Pressure Chemical Ionization
1.13 Atmospheric Pressure Photoionization (APPI)
1.14 Atmospheric Pressure Secondary Ion Mass Spectrometry (APSIMS)
1.14.1 Desorption electrospray ionization (DESI)
1.14.2 Direct analysis in real time (DART)
1.15 Inorganic Ionization Sources
1.15.1 Thermal ionization source
1.15.2 Spark source
1.15.3 Glow discharge source
1.15.4 Inductively coupled plasma source
1.15.5 Practical considerations
1.16 Gas-Phase Ion-Molecule Reactions
1.17 Formation and Fragmentation of Ions: Basic Rules
1.17.1 Electron ionization and photoionization under vacuum
1.17.2 Ionization at low pressure or at atmospheric pressure
1.17.3 Proton transfer
1.17.4 Adduct formation
1.17.5 Formation of aggregates or clusters
1.17.6 Reactions at the interface between source and analyzer
2 Mass Analyzers
2.1 Quadrupole Analyzers
2.1.1 Description
2.1.2 Equations of motion
2.1.3 Ion guide and collision cell
2.1.4 Spectrometers with several quadrupoles in tandem
2.2 Ion Trap Analyzers
2.2.1 Three-dimensional ion trap
2.2.2 Two-dimensional ion trap
2.3 The Electrostatic Trap or “Orbitrap”
2.4 Time-of-Flight Analyzers
2.4.1 Linear time-of-flight mass spectrometer
2.4.2 Delayed pulsed extraction
2.4.3 Reflectrons
2.4.4 Tandem mass spectrometry with time-of-flight analyzer
2.4.5 Orthogonal acceleration time-of-flight instruments
2.5 Magnetic and Electromagnetic Analyzers
2.5.1 Action of the magnetic field
2.5.2 Electrostatic field
2.5.3 Dispersion and resolution
2.5.4 Practical considerations
2.5.5 Tandem mass spectrometry in electromagnetic analyzers
2.6 Ion Cyclotron Resonance and Fourier Transform Mass Spectrometry
2.6.1 General principle
2.6.2 Ion cyclotron resonance
2.6.3 Fourier transform mass spectrometry
2.6.4 MSn in ICR/FTMS instruments
2.7 Hybrid Instruments
2.7.1 Electromagnetic analyzers coupled to quadrupoles or ion trap
2.7.2 Ion trap analyzer combined with time-of-flight or ion cyclotron resonance
2.7.3 Hybrids including a time-of-flight with orthogonal acceleration
3 Detectors and Computers
3.1 Detectors
3.1.1 Photographic plate
3.1.2 Faraday cup
3.1.3 Electron multipliers
3.1.4 Electro-optical ion detectors
3.2 Computers
3.2.1 Functions
3.2.2 Instrumentation
3.2.3 Data acquisition
3.2.4 Data conversion
3.2.5 Data reduction
3.2.6 Library search
4 Tandem Mass Spectrometry (MS/MS)
4.1 Tandem Mass Spectrometry in Space or in Time
4.2 Tandem Mass Spectrometry Scan Modes
4.3 Collision-activated or Collision-induced Dissociation (CAD or CID)
4.3.1 Collision energy conversion to internal energy
4.3.2 High-energy collision (keV)
4.3.3 Low-energy collision (between 1 and 100 eV)
4.4 Other Methods of Ion Activation
4.5 Reactions Studied in MS/MS
4.6 Tandem Mass Spectrometry Applications
4.6.1 Structure elucidation
4.6.2 Selective detection of target compound class
4.6.3 Ion–molecule reaction
4.6.4 The kinetic method
5 Mass Spectrometry/Chromatography Coupling
5.1 Elution Chromatography Coupling Techniques
5.1.1 Gas chromatography/mass spectrometry (GC/MS)
5.1.2 Liquid chromatography/mass spectrometry (LC/MS)
5.1.3 Capillary electrophoresis/mass spectrometry (CE/MS)
5.2 Chromatography Data Acquisition Modes
5.3 Data Recording and Treatment
5.3.1. Data recording
5.3.2 Instrument control and treatment of results
6 Analytical Information
6.1 Mass Spectrometry Spectral Collections
6.2 High Resolution
6.2.1 Information at different resolving powers
6.2.2 Determination of the elemental composition
6.3 Isotopic Abundances
6.4 Low-mass Fragments and Lost Neutrals
6.5 Number of Rings or Unsaturations
6.6 Mass and Electron Parities, Closed-shell Ions and Open-shell Ions
6.6.1 Electron parity
6.6.2 Mass parity
6.6.3 Relationship between mass and electron parity
6.7 Quantitative Data
6.7.1 Specificity
6.7.2 Sensitivity and detection limit
6.7.3 External standard method
6.7.4 Sources of error
6.7.5 Internal standard method
6.7.6 Isotopic dilution method
7 Fragmentation Reactions
7.1 Electron Ionization and Fragmentation Rates
7.2 Quasi-equilibrium and RRKM Theory
7.3 Ionization and Appearance Energies
7.4 Fragmentation Reactions of Positive Ions
7.4.1 Fragmentation of odd-electron cations or radical cations (OE.+)
7.4.2 Fragmentation of cations with an even number of electrons (EE+)
7.4.3 Fragmentations obeying the parity rule
7.4.4 Fragmentations not obeying the parity rule
7.5 Fragmentation Reactions of Negative Ions
7.5.1 Fragmentation mechanisms of even electron anions (EE–)
7.5.2 Fragmentation mechanisms of radical anions (OE. –)
7.6 Charge Remote Fragmentation (CRF)
7.7 Spectrum Interpretation
7.7.1 Typical ions
7.7.2 Presence of the molecular ion
7.7.3 Typical neutrals
7.7.4 A few examples of the interpretation of mass spectra
8 Analysis of Biomolecules
8.1 Biomolecules and Mass Spectrometry
8.2 Proteins and Peptides
8.2.1 ESI and MALDI
8.2.2 Structure and sequence determination using fragmentation
8.2.3. Applications
8.3. Oligonucleotides
8.3.1. Mass Spectra of Oligonucleotides
8.3.2. Applications of Mass Spectrometry to Oligonucleotides
8.3.3. Fragmentation of Oligonucleotides
8.3.4. Characterization of Modified Oligonucleotides
8.4. Oligosaccharides
8.4.1. Mass Spectra of Oligosaccharides
8.4.2. Fragmentation of Oligosaccharides
8.4.3. Degradation of Oligosaccharides Coupled with Mass Spectrometry
8.5. Lipids
8.5.1. Fatty Acids
8.5.2 Acylglycerols
8.5.3. Bile Acids
8.6 Metabolomics
8.6.1 Mass spectrometry in metabolomics
8.6.2 Applications
9 Exercises
A. Questions
B. Answers
Appendices
Appendix 1. Nomenclature
1.1. Units
1.2. Definitions
1.3. Analyzers
1.4. Detection
1.5. Ionization
1.6 Ion Types
1.7. Ion–molecule Reaction
1.8. Fragmentation
Appendix 2. Abbreviations
Appendix 3. Fundamental Physical Constants
Appendix 4A . Table of Isotopes in Ascending Mass Order
Appendix 4B. Table of Isotopes in Alphabetical Order
Appendix 5. Isotopic Abundances in 0.000000or Various Elemental Compositions CHON (M = 100%)
Appendix 6. Gas-Phase Ion Thermochemical Data of Molecules
Appendix 7. Gas-Phase Ion Thermochemical Data of Radicals
Appendix 8. Literature on Mass Spectrometry
Appendix 9. Mass Spectrometry on Internet
Index