1st Edition

Assigning Structures to Ions in Mass Spectrometry

    466 Pages
    by CRC Press

    472 Pages 104 B/W Illustrations
    by CRC Press

    Summarizing our present knowledge of the structures and chemistry of small organic cations in the gas phase, Assigning Structures to Ions in Mass Spectrometry presents the methods necessary for determining gas-phase ion structures. It is a comprehensive resource of background material that is essential for the interpretation and understanding of organic mass spectra.

    Following a historical introduction of chief discoveries, the book surveys current experimental methods for ion production and separation as well as those designed to reveal qualitative and quantitative aspects of gas-phase ions. It also examines the computational chemistry and theoretical calculations that provide complementary thermochemical, structural, and mechanistic information. Five selected case studies illustrate specific challenges associated with ion structure assignment and thermochemical problems. The last major section of the book contains the data for describing or identifying all ions containing C alone and C with H, O, N, S, P, halogens, and small organic cations.

    Presenting material written by leading researchers in the field, Assigning Structures to Ions in Mass Spectrometry underscores the importance of understanding the behavior of small organic ions and gas-phase ion chemistry for making new ion structure assignments

    PART I: THEORY AND METHODS

    Tools for Identifying the Structure of Gas-Phase Ions
    Introduction
    How Ions Are Generated and Separated for Analysis
    Thermochemistry-Its Role in Assigning Ion Structures
    Experiments with Mass-Selected Ions
    Reactivity of Ions; Another Tool for Ion Structure Determination
    Use of Computational Chemistry in Ion Structure Determination

    What and What Not to Expect from Gas-Phase Ions
    Introduction
    Identification of a New Class of Ions: Distonic Ions
    The McLafferty Rearrangement: A Concerted or Stepwise Process?
    Peptide Ion Fragmentation: The Structure of b-Type Ions
    The Need for Computational Chemistry: The Methylacetate Ion Story
    A Problem with Neutral Thermochemistry: DfH(CH3CH2OOH) Revisited
    Some Advice When Assigning Structures to Gas-Phase Ions

    References to Part 1

    PART II: IONS CONTAINING C AND POLYATOMIC IONS CONTAINING ONE TO THREE C ATOMS

    Ion Structures
    Introduction
    Thermochemical Data
    Ions Containing Only Carbon Atoms
    Isomers/Identification
    References
    Ions Containing One Carbon Atom
    References
    Ions Containing Three Carbon Atoms

    Index of C1 to C3 Ion Formulae
    Index

    Biography

    John L. Holmes, Christiane Aubry, Paul M. Mayer

    "There is no comparable combination of an in-depth discussion and a comprehensive compendium of thermochemical data of organic ions. … warmly recommended to all scientists who are interested and/or work in fields connected with mass spectrometry. … warmly recommended to all scientists who are interested and/or work in fields connected with mass spectrometry. … I recommend it for all who look at mass-spectral peaks— whatever m/z—with curiosity!"
    Anal Bioanal Chem (2008) 390:429–431