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  • Digitale Medien  (2)
  • Analytical Chemistry and Spectroscopy  (2)
  • 1
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 24 (1989), S. 875-884 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Under electron ionization (EI) conditions, porphyrins yield unusually high intensities of doubly charged molecular and fragment ions. These doubly charged ions offer unique opportunities for the structure elucidation of porphyrins by tandem mass spectrometry (MS/MS). First, they fragment to a greater extent than the corresponding singly charged ions under both EI/MS and EI/MS/MS conditions. Second, doubly and singly charged porphyrin ions often fragment via different pathways, and can therefore yield different structural information. This paper describes several ways in which analyses of doubly charged porphyrin ions with a triple quadrupole tandem mass spectrometer can be useful in structure elucidation of porphyrins. The effect of the metal atom on the fragmentation of metalloporphyrins in an EI source is demonstrated by correlating the extent of doubly charged fragment ion formation to a stability index. Doubly charged porphyrin ions are shown to yield predominantly doubly charged daughter ions upon collisionally activated dissociation (CAD), and are also shown to fragment to a greater extent than corresponding singly charged porphyrin ions. Advantages and disadvantages of doubly charged porphyrin ion MS/MS for structure elucidation are discussed.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 20 (1991), S. 245-254 
    ISSN: 0049-8246
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: A mathematical model has been developed for the quantitative x-ray fluorescence spectrometry of small spherical samples, e.g. targets containing diagnostic materials for inertial confinement fusion experiments. The model corrects for matrix effects in a multi-layer spherical geometry much as existing programs now do for thin films or bulk samples. Attenuation effects have been found to be greater in a shell geometry than in a comparable thin-film geometry because multiple passes through the shell are possible and because many paths in or out are nearly tangential to the shell. In both cases the path is longer and attenuation is greater. The model for primary fluorescence from uniform shells has also been extended to approximate the fluorescence from non-uniform shells. This allows one to predict how experimental results would vary with sample mounting if excess material were oriented toward or away from the x-ray beam or the detector or away from both. Finally, a simplified model for estimating the magnitude of secondary fluorescence effects is presented.
    Zusätzliches Material: 16 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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