Four decades of joy in mass spectrometry

N.M.M. Nibbering

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    Tremendous developments in mass spectrometry have taken place in the last 40 years. This holds for both the science and the instrumental revolutions in this field. In chemistry the research was heavily focused on organic molecules that upon electron ionization fragmented via complex mechanistic pathways as shown by isotopic labeling experiments. These studies, including ion structure determinations, were performed with use of double focusing mass spectrometers of both conventional and reversed geometry, and equipped with various types of metastable ion scanning and collision-induced dissociation techniques developed by physical and analytical chemists. Time-resolved mass spectrometry by use of the field ionization kinetics method, developed by physical chemists, was another powerful way to unravel details of unimolecular gas phase ion dissociations. Then the development of new ionization methods, such as desorption chemical ionization, field desorption, and fast atom bombardment permitted not only to analyze unvolatile, thermally labile and higher molecular weight compounds, but also to study their chemical behavior in the gas phase, initially with use of double focusing instruments and later on with multisector and hybrid mass spectrometers. These ionization methods also enabled to study organometallic compounds and increasingly the field of medium-sized to large biomolecules, the latter being exploded in the last decade by the development of electrospray- and matrix-assisted laser desorption ionization/time-of-flight mass spectrometry. Another area of research concerned the bimolecular chemistry of organic ions with organic molecules in the gas phase. Initially this was performed with use of among others drift-cell ion cyclotron resonance spectroscopy, that later on was replaced by the developed method of ion trapping and Fourier transform ion cyclotron resonance. Combination of the latter with the afore-mentioned ionization methods has shifted also in this case the research on organic molecules to organometallic/inorganic systems, and predominantly to biomolecules in the last decade. This invited review will describe the research efforts made by the author's group over the last 40 years together with some personal experiences during his career.
    Original languageUndefined
    Pages (from-to)962-1017
    JournalMass Spectrometry Reviews
    Issue number6
    Publication statusPublished - 2006


    • stereochemistry
    • reaction mechanisms
    • pyrolysis mass spectrometry
    • radicals
    • IR-72095
    • Collision-induced dissociation
    • Fourier transform ion cyclotron resonance
    • Fullerenes
    • Gas-phase ion chemistry
    • Ion structures
    • Ion/molecule reactions
    • negative ions
    • positive ions
    • field desorption
    • field ionization kinetics
    • biomolecules
    • supramolecular systems
    • thermochemistry
    • density functional theory
    • stable isotopic labeling

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