Elimination of the concentration dependence in mass isotopomer abundance mass spectrometry of methyl palmitate using metastable atom bombardment View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2001-06-01

AUTHORS

Clifton K. Fagerquist, Marc K. Hellerstein, Denis Faubert, Michel J. Bertrand

ABSTRACT

An important problem in mass isotopomer abundance mass spectrometry (MIAMS) is the dependence of measured mass isotopomer abundances on sample concentration. We have evaluated the role of ionization energy on mass isotopomer abundance ratios of methyl palmitate as a function of sample concentration. Ionization energy was varied using electron impact ionization (EI) and metastable atom bombardment (MAB). The latter generates a beam of metastable species capable of ionizing analyte molecules by Penning ionization. We observed that ionization of methyl palmitate by EI (70 eV) showed the greatest molecular ion fragmentation and also showed the greatest dependence of relative isotopomer abundance ratios on sample concentration. Ionization using the 3P2 and 3P0 states of metastable krypton (9.92 and 10.56 eV, respectively) resulted in almost no molecular ion fragmentation, and the isotopomer abundances quantified were essentially independent of sample concentration. Ionization using the 3P2 and 3P0 states of metastable argon (11.55 and 11.72 eV, respectively) showed molecular ion fragmentation intermediate between that of EI and MAB(Kr) and showed an isotopomer concentration dependence which was less severe than that observed with EI but more severe than that observed with MAB(Kr). The observed decrease in the dependence of isotopomer abundance on sample concentration with a decrease in molecular ion fragmentation is consistent with the hypothesis that proton transfer from a fragment cation to a neutral molecule is the gas phase reaction mechanism responsible for the concentration dependence. Alternative explanations, e.g., hydrogen abstraction from a neutral molecule to a molecular cation, is not supported by these results. Moreover, the MAB ionization technique shows potential for eliminating one source of error in MIAMS measurements of methyl palmitate, in particular, and of fatty acids methyl esters, in general. More... »

PAGES

754-761

References to SciGraph publications

  • 2000-09-01. Proton affinities of saturated aliphatic methyl esters in JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
  • 1999-05-01. Molecular ion fragmentation and its effects on mass isotopomer abundances of fatty acid methyl esters ionized by electron impact in JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
  • 1927-10. Über Ionisation durch metastabile Atome in THE SCIENCE OF NATURE
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  • Identifiers

    URI

    http://scigraph.springernature.com/pub.10.1016/s1044-0305(01)00227-6

    DOI

    http://dx.doi.org/10.1016/s1044-0305(01)00227-6

    DIMENSIONS

    https://app.dimensions.ai/details/publication/pub.1053222022

    PUBMED

    https://www.ncbi.nlm.nih.gov/pubmed/11401166


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    168 rdf:type schema:Organization
     




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