Mass Spectrometry A Textbook by Jürgen H. Gross (informative)
Free download Mass Spectrometry A Textbook by Jürgen H. Gross
3rd edition
Authors of: Mass Spectrometry A Textbook by Jürgen H. Gross
Jürgen H. Gross
Table of Contents in Mass Spectrometry A Textbook by Jürgen H. Gross
1 Introduction
1.1 Mass Spectrometry: Versatile and Indispensable
1.2 Historical Sketch
1.2.1 The First Mass Spectra
1.2.2 Thomson’s Parabola Spectrograph
1.2.3 Milestones
1.3 Aims and Scope of This Textbook
1.3.1 Facets of Mass Spectrometry
1.4 What Is Mass Spectrometry?
1.4.1 Basic Principle of Mass Spectrometry
1.4.2 Mass Spectrometer
1.4.3 Mass Scale
1.4.4 Mass Spectrum
1.4.5 Statistical Nature of Mass Spectra
1.4.6 Bars, Profiles, and Lists
1.5 Ion Chromatograms
1.6 Performance of Mass Spectrometers
1.6.1 Sensitivity
1.6.2 Limit of Detection
1.6.3 Signal-to-Noise Ratio
1.7 Terminology – General Aspects
1.7.1 Basic Terminology in Describing Mass Spectra
1.8 Units, Physical Quantities, and Physical Constants
1.9 Further Reading
1.10 Quintessence
References
2 Principles of Ionization and Ion Dissociation
2.1 Gas Phase Ionization by Energetic Electrons
2.1.1 Formation of Ions
2.1.2 Processes Accompanying Electron Ionization
2.1.3 Ions Generated by Penning Ionization
2.1.4 Ionization Energy
2.1.5 Ionization Energy and Charge-Localization
2.2 Vertical Transitions
2.3 Ionization Efficiency and Ionization Cross Section
2.4 Internal Energy and the Further Fate of Ions
2.4.1 Degrees of Freedom
2.4.2 Appearance Energy
2.4.3 Bond Dissociation Energies and Heats of Formation
2.4.4 Randomization of Energy
2.5 Quasi-Equilibrium Theory
2.5.1 QET’s Basic Premises
2.5.2 Basic QET
2.5.3 Rate Constants and Their Meaning
2.5.4 k(E) Functions – Typical Examples
2.5.5 Reacting Ions Described by k(E) Functions
2.5.6 Direct Cleavages and Rearrangement Fragmentations
2.6 Time Scale of Events
2.6.1 Stable, Metastable, and Unstable Ions
2.6.2 Time Scale of Ion Storage Devices
2.7 Internal Energy – Practical Implications
2.8 Reverse Reactions – Activation Energy and Kinetic Energy Release
2.8.1 Activation Energy of the Reverse Reaction
2.8.2 Kinetic Energy Release
2.8.3 Energy Partitioning
2.9 Isotope Effects
2.9.1 Primary Kinetic Isotope Effects
2.9.2 Measurement of Isotope Effects
2.9.3 Secondary Kinetic Isotope Effects
2.10 Determination of Ionization Energies
2.10.1 Conventional Determination of Ionization Energies
2.10.2 Improved IE Accuracy from Data Post-processing
2.10.3 IE Accuracy – Experimental Improvements
2.10.4 Photoionization Processes
2.10.5 Photoelectron Spectroscopy and Derived Methods
2.10.6 Mass-Analyzed Threshold Ionization
2.11 Determining the Appearance Energies
2.11.1 Kinetic Shift
2.11.2 Breakdown Graphs
2.12 Gas Phase Basicity and Proton Affinity
2.13 Ion–Molecule Reactions
2.13.1 Reaction Order
2.13.2 Solution Phase Versus Gas Phase Reactions
2.14 Summary of Gas Phase Ion Chemistry
References
3 Isotopic Composition and Accurate Mass
3.1 Isotopic Classification of the Elements
3.1.1 Monoisotopic Elements
3.1.2 Di-isotopic Elements
3.1.3 Polyisotopic Elements
3.1.4 Representation of Isotopic Abundances
3.1.5 Calculation of Atomic, Molecular, and Ionic Mass
3.1.6 Natural Variations in Relative Atomic Mass
3.2 Calculation of Isotopic Distributions
3.2.1 Carbon: An X + 1 Element
3.2.2 Terms Related to Isotopic Composition
3.2.3 Binomial Approach
3.2.4 Halogens
3.2.5 Combinations of Carbon and Halogens
3.2.6 Polynomial Approach
3.2.7 Oxygen, Silicon, and Sulfur
3.2.8 Polyisotopic Elements
3.2.9 Practical Aspects of Isotopic Patterns
3.2.10 Bookkeeping with Isotopic Patterns in Mass Spectra
3.2.11 Information from Complex Isotopic Patterns
3.2.12 Systematic Approach to Reading Isotopic Patterns
3.3 Isotopic Enrichment and Isotopic Labeling
3.3.1 Isotopic Enrichment
3.3.2 Isotopic Labeling
3.4 Resolution and Resolving Power
3.4.1 Definitions
3.4.2 Resolution and Its Experimental Determination
3.4.3 Resolving Power and Its Effect on Relative Peak Intensity
3.5 Accurate Mass
3.5.1 Exact Mass and Molecular Formulas
3.5.2 Relativistic Mass Defect
3.5.3 Role of Mass Defect in Mass Spectrometry
3.5.4 Mass Accuracy
3.5.5 Accuracy and Precision
3.5.6 Mass Accuracy and the Determination of Molecular Formulas
3.5.7 Extreme Mass Accuracy: Special Considerations
3.6 Applied High-Resolution Mass Spectrometry
3.6.1 Mass Calibration
3.6.2 Performing an External Mass Calibration
3.6.3 Internal Mass Calibration
3.6.4 Specification of Mass Accuracy
3.6.5 Identification of Formulas from HR-MS Data
3.7 Resolution Interacting with Isotopic Patterns
3.7.1 Multiple Isotopic Compositions at Very High Resolution
3.7.2 Isotopologs and Accurate Mass
3.7.3 Large Molecules – Isotopic Patterns at Sufficient Resolution
3.7.4 Isotopic Patterns of Macromolecules Versus Resolution
3.8 Charge State and Interaction with Isotopic Patterns
3.9 Approaches to Visualize Complex HR-MS Data Sets
3.9.1 Deltamass
3.9.2 Kendrick Mass Scale
3.9.3 Van Krevelen Diagrams
3.10 Vantage Point on the World of Isotopes and Masses
References
4 Instrumentation
4.1 How to Create a Beam of Ions
4.2 Time-of-Flight Instruments
4.2.1 Time-of-Flight: Basic Principles
4.2.2 TOF Instruments: Velocity of Ions and Time-of-Flight
4.2.3 Linear Time-of-Flight Analyzer
4.2.4 Better Vacuum Improves Resolving Power
4.2.5 Energy Spread of Laser-Desorbed Ions
4.2.6 Reflector Time-of-Flight Analyzer
4.2.7 Delay Before Extraction to Improve Resolving Power
4.2.8 Orthogonal Acceleration TOF Analyzers
4.2.9 Operation of the oaTOF Analyzer
4.2.10 Duty Cycle
4.2.11 TOF Analyzers with a Folded Eight-Shaped Flight Path
4.2.12 Multi-reflecting TOFs
4.2.13 Essence of TOF Instruments
4.3 Magnetic Sector Instruments
4.3.1 Evolution of Magnetic Sector Instruments
4.3.2 Principle of the Magnetic Sector
4.3.3 Focusing Action of the Magnetic Field
5 Practical Aspects of Electron Ionization
5.1 Electron Ionization Ion Sources
5.1.1 Layout of an Electron Ionization Ion Source
5.1.2 Generation of Primary Electrons
5.1.3 Overall Efficiency and Sensitivity of an El Ion
5.1.4 Optimization of Ion Beam Geometry
5.1.5 Mounting the Ion Source
5.2 Sample Introduction
5.2.1 Reservoir or Reference Inlet System
5.2.2 Direct Insertion Probe
5.2.3 Sample Vials for Use with Direct Insertion Probes
5.2.4 How to Run a Measurement with a Direct Insertion
5.2.6 Fractionation When Using Direct Insertion Probes
5.2.7 Direct Exposure Probe
5.3 Pyrolysis Mass Spectrometry
5.4 Gas Chromatograph
5.5 Liquid Chromatograph
5.6 Low-Energy Electron Ionization Mass Spectra
5.7 Analytes for EI
5.8 Mass Analyzers for EI
5.9 Mass Spectral Databases for EI
5.9.1 NIST/EPA/NIH Mass Spectral Database
5.9.2 Wiley Registry of Mass Spectral Data
5.9.3 Mass Spectral Databases: General Aspects
5.10 EI in a Nutshell
References
6 Fragmentation of Organic Ions and Interpretation of EI
Mass Spectra
7 Chemical Ionization
8 Field Ionization and Field Desorption
9 Tandem Mass Spectrometry
10 Fast Atom Bombardment
11 Matrix-Assisted Laser Desorption/Ionization
12 Electrospray Ionization
13 Ambient Desorption/Ionization
14 Hyphenated Methods
15 Inorganic Mass Spectrometry
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