The Encyclopedia of Mass Spectrometry - 1st Edition - ISBN: 9780080438016

The Encyclopedia of Mass Spectrometry

1st Edition

Volume 6: Ionization Methods

Editors: Michael L. Gross Richard M. Caprioli
Hardcover ISBN: 9780080438016
Imprint: Elsevier Science
Published Date: 18th December 2006
Page Count: 1030
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Volume 6: Ionization Methods captures the story of molecular ionization and its phenomenal evolution that makes mass spectrometry the powerful method it is today. Chapters 1 and 2 cover fundamentals and various issues that are common to all ionization (e.g., accurate mass, isotope clusters, and derivatization).

Chapters 3-9 acknowledge that some ionization methods are appropriate for gas-phase molecules and others for molecules that are in the solid or liquid states. Chapters 3-6 cover gas-phase molecules, dividing the subject into: (1) ionization of gas-phase molecules by particles (e.g., EI), (2) ionization by photons, (3) ionization by ion-molecule and molecule-molecule reactions (e.g., APCI and DART), and ionization in Strong electric fields (i.e., Electrohydrodynamic and Field Ionization/Desorption).

"Ionization in a Strong Electric Field" illustrates the transition to ionization of molecules in the solid or liquid states, covered in Chapters 7-9: (1) spray methods for ionization (e.g., electrospray), (2) desorption ionization by particle bombardment (e.g., FAB), and (3) desorption by photons (e.g., MALDI). Electrospray and MALDI also lead to applications in biophysical chemistry, the theme of Chapter 10.

Chapter 11 reconsiders ionization from the view of choosing an ionization method. The range of subjects is from ionization of organic and biomolecules to the study of microorganisms.

Key Features

  • Reviews range of ionization methods used in mass spectrometry today
  • Includes tutorials describing the principles and instrumentation applied to each method
  • Considers appropriate methods of ionization for analysis of various substances


Advanced research scientists, mass spectrometrists, spectroscopists, analytical chemists and those working in related fields

Table of Contents

Chapter 1 Fundamentals of Ionization
Ionization Energies (Adam Bruskern and M L Gross)
Gas-phase Basicities and Proton Affinities (J Bartmess)
Gas-Phase Acidities (J Bartmess)
Electron Affinities (J Bartmess)
Metal-Cation Affinities (G Ohanessian and Y Hoppilliard)

Chapter 2 General Considerations for Ionization
Odd and Even Electron Ions and Their Role in Assigning Molecular Ions (M Wilcox and M L Gross)
The Nitrogen Rule (L Frevel)
Isotope patterns (A Goraczko)
Accurate-mass Measurements (R Kondrat)
Sample Handling and Inlet systems (M Grayson)
Derivatization for mass spectrometry (J.M Halket, V Zaikin)

Chapter 3 Ionization of Gas-Phase Molecules by Particles and at High Temperature: Electron Ionization (EI), Positron Ionization, and Surface Ionization Organic
Electron Ionization (EI): Principles and Instrumentation (J Traeger)
In-beam EI and desorption EI (K Miyabayashi)
Electron Ionization and Supersonic Molecular Beams (M.L Gross )
EI mass spectra of classes of organic compounds (N Glagovich)
Identification of Unknown EI Mass Spectra Using Library Searches and EI Mass Spectral Databases (D Sparkman)
Positron Ionization: Principles and Instrumentation (G Glish)
Surface Ionization Organic Mass Spectrometry: Principles and instrumentation (T Fujii)

Chapter 4 Ionization of Gas-Phase Molecules by Photons: Photoionization (PI), Photoelectron Spectroscoy (PES) and Laser Ionization
Photo ionization: Principles and Instrumentation (J Traeger)
Atmospheric Pressure Photoionization: Basic Principles (A Raffaelli)
Dopant-Assisted Atmospheric pressure Photoionization (R Kostininen.)
Photoelectron Spectroscopy: Principles and Instrumentation (J Traeger)
Laser Ionization: Principles and Instrumentation (J Reilly)
Resonance Enhanced Multiphoton Ionization of neutrals in supersonic beams (T Benter)
Atmospheric Pressure Laser Ionization (T Benter)
High Resolution Ion Spectroscopy in Mass Spectrometry (J Grotemeyer)
Photoionization of desorbed neutrals from surfaces (M Ahmed)
Photoionization of jet cooled molecules (M de Vries)
Organic Particle Analysis off a Surface (M Johnston)

Chapter 5 Ionization by Ion-Molecule and Molecule-Molecule Reactions: Chemical Ionization (CI), Atmospheric Pressure Chemical Ionization (APCI), and DART
Chemical Ionization: Principles, Instrumentation, and Applications (H Rohrs)
Resonance Electron Capture Mass Spectrometry (M Deinzer)
Chemical Ionization: Transfer of Other Groups (J Brodbelt)
Chemical Ionization (CI): Transfer of or Reaction with Metal Ions (D Peake)
Ion Attachment mass spectrometry (T Fujii)
Cluster Chemical Ionization (M Gross)
Photoelectron resonance capture ionization (G A Petrucci)
Atmospheric Pressure Chemical Ionization: Principles, Instrumentation, and Applications (M Moini)
Atmospheric pressure microwave induced plasma ionization (M Moini)
The Heated Nebulizer LC/MS Interface (B Thomson)
Surface Activated ("no discharge") Atmospheric Pressure Chemical Ionization (S Cristoni)
Chemi-ionization and Direct Analysis in Real Time (DARTtm) Mass Spectrometry (C Cody)

Chapter 6 Ionization in Strong Electric Field
Field Ionization and Field Desorption: Principles, Instrumentation, and Applications (M L Gross)
Electrohydrodynamic Ionization: Principles, Instrumentation, and Applications (K Cook)

Chapter 7 Spray Methods for Ionization
Thermospray: Perspectives on Invention and Mechanism (M Vestal)
Thermospray Ionization: Principles and instrumentation (W Budde)
Electrospray ionization: Principles and Instrumentation (K Cook, A Bruins)
Electrochemistry of the Electrospray Ionization Source (G van Berkel)
Pneumatically assisted Electrospary Ionization (T Covey)
Micro and Nano-Electrospray Ionization Techniques (B Thomson)
Electrospray Ionization with organic metal and related emitters (T Wood)
Pulsed Electrospray Ionization (M L Gross)
Multiple Sprayers in Electrospray Ionization (B Schneider and T Covey)
Energy-dependent ESI (J S McIndoe)
Charge State Manipulation in Spray Ionization (S McLuckey)
Sonic Spray Ionization (A Hirabayashi )
Electrosonic Spray Ionization (Z Takats and R G Cooks)
Electrospray Ionization with Venturi and related Devices (R G Cooks)
Cold-spray ionization (K Yamaguchi)
Laser spray Ionization (J Sunner)
Studies of Single Droplets Having Net Charge (G Agnes)
Fused-Droplet Electrospray Ionization and Electrospray Laser Desorption Ionization (J Sunner)
Extractive electrospray ionization (R G Cooks)

Chapter 8 Desorption Ionization by Particle Bombardment: SIMS, Fast Atom Bombardment, and High-Energy Beams
Secondary Ioniztion Mass Spectrometry and Fast Atom Bombardment: Principles and Instrumentation (A Walker)
Ion and Atom Guns (J Delmore)
Massive Particle Bombardment (J Delmore)
Continuous-flow Fast Atom Bombardment (R Caprioli)
Pulsed Fast Atom Bombardment (M Grayson)
Chemical Ionization Fast-Atom Bombardment. (J Callahan)
Chemical reactions induced by FAB and LSIMS (G Santana Marques)
Desorption Electrospay Ionization (Z Takats and R.G Cooks)
Electrospray droplet impact/secondary ion mass spectrometry (K Hiraoka)
Secondary Ionization Mass Spectrometry for Imaging (N Winograd)
Desorption by Cf-252 Fission Fragments (R MacFarlane and Y LeBeyec)
Desorption by Ion Beams from Accelerators (R MacFarlane and Y LeBeyec)

Chapter 9 Desorption by Photons: Laser Desorption and Matridx-Assisted Laser Desorption Ionization (MALDI)
Laser Desorption: Principles and Instrumentation (H Rohrs)
Laser Desorption-Atmospheric Pressure Chemical Ionization (J Coon)
Hyperthermal surf ionization of laser-desorbed species (M L Gross)
UV Matrix-Assisted Laser Desorption Ionization: Principles, Instrumentation, and Applications (R Cramer and Klaus Dreisewerd)
Matrix-Assisted Laser Desorption Ionization: Matrix design, choice, and application (J Gross )
Ionic Liquids as matrices for Matrix-Assisted Laser Desorption Ionization (Y Li)
Desorption/Ionization on Silicon (DIOS) (G Siuzdak)
Solvent-free Matrix-Assisted Laser Desorption Ionization (M Deinzer and S Trimpin)
Droplet Levitation as an Enabling Strategy for Pico-liter Sample Manipulation (G Agnes)
Atmospheric Pressure Matrix Assisted Laser Desorption Ionization (AP-MALDI) (V Laiko)
Infrared Matrix-Assisted Laser Desorption Ionization (K Murray)
Surface Enhanced Laser Desorption Ionization Mass Spectrometry (SELDI-MS) (S L McCutchen-Maloney)
Surface Matrix-Assisted Laser Desorption Ionization (H J Griesser)
Comparative DNA Sequence Analysis by MALDI (D van den Boom )

Chapter 10 Biophysical Application of Desorption and Spray Ionization
Biopolymer Ions in a Solvent-Free Environment (I Kaltashov)
Macromolecular Conformations in Solution from Charge-State Distributions Produced by Electrospray Ionization (I Kaltashov)
Large non-covalent biological complexes (C Robinson and T Videler)
H/D Amide Exchange Matrix-Assisted Laser Desorption Ionization: Analysis of Protein-Protein Interfaces (E Komives)
Direct Mass Spectrometric Methods for Determining Affinity (R Chitta)
Protein-Ligand Interactions in solution by Mass Spectrometry, Titration and H/D Exchange (PLIMSTEX) (M Zhu)
Self Association Interactions using Mass Spectrometry, Self Titration, and H/D Exchange (SIMSTEX) (R Chitta, )
Stability of Unpurified Proteins from Rates of H/D Exchange (SUPREX) Analysis of Protein Folding and Function (M Fitzgerald)
Time-resolved Electrospray Ionization (L Konermann.)
Protein-Carbohydrate Affinities: An Example of a Direct Method to Determine Equilibrium Constants (J S Klassen)
Chemical Crosslinking for Protein Structure Characterization (A Sinz)
Chemical Foot Printing of Proteins: – OH Reactions (D Hambly and M L Gross)

Chapter 11 Choice of Ionization for Analysis of Various Substances
Typical Classes of Organic Molecules (M Wilcox and M L Gross)
Natural Products (Y Wang and H-h Hong)
Peptides and Proteins (C Dass)
Oligonucleotides (P Limbach)
Free Fatty Acids and Lipids (X Han and R Gross)
Carbohydrates (J Zaia)
Organometallics (J S McIndoe)
Synthetic Polymers (S Hanton )
Pyrolysis Mass Spectrometry (J Hacaloglu)
Microorganisms (J Lay)
On-line Organic Aerosol Analysis (G A Petrucci)


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About the Editor

Michael L. Gross

Michael L. Gross is Professor of Chemistry and Professor of Medicine at Washington University, St. Louis, as well as Director of the NIH Mass Spectrometry Research Resource located at Washington University.

1966: Ph.D., University of Minnesota
1987: Commonwealth of Massachusetts Pioneer Award, "In Search of the Health Consequences of Dioxin in Our Environment"
1983 -1991: Identified as one of the 50 most cited chemists
1999: Field and Franklin Award of The American Chemical Society
2001: Outstanding Graduate Student Mentor, Washington University

Affiliations and Expertise

Washington University, St Louis, USA

Richard M. Caprioli

Biography Richard M. Caprioli is the Stanley Cohen Professor of Biochemistry and Director of the Mass Spectrometry Research Center at Vanderbilt University School of Medicine. He is also currently Professor in the Departments of Chemistry and Pharmacology at Vanderbilt.

Affiliations and Expertise

Vanderbilt University School of Medicine, Nashville, USA

Ratings and Reviews