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  • 1995-1999  (3)
  • 1
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The responses of selected-ion monitoring of electron impact mass spectra and selected-reagent-ion chemical ionization mass spectra of polychlorinated biphenyls (PCBs), relative to that of congener 153, have been determined for some 60 PCBs contained in four standard mixtures. The PCB congeners examined cover a wide range of toxicities. Average responses have been determined for PCBs as a function of both the total number of chlorine substituents and the number of ortho-substituents. Average relative responses and relative responses of individual congeners have been compared with Literature values of relative responses obtained by electron-capture detection. Detection limits for electron ionization and C2H5+ chemical ionization mass spectrometry, determined as the mass of congener 153 injected on column and yielding a signal-to-noise ratio of 5:1 were 0.76 pg and 30 pg, respectively, compared to some 70 fg for electron-capture detection. An initial exploration and evaluation have been carried out, of the potential value of using a toxicity index to define the total toxicity of a sample; such an index is based on 39 non- and mono-ortho substituted PCBs. Electron ionization, when combined with selected-ion monitoring of both molecular and fragment ions, is the more sensitive mass-selective method for the determination of the most toxic PCB congeners.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The gas-phase behaviour of organophosphorus compounds such as diethylmethylphosphonate towards electron impact (EI) ionization occurring in a quadrupole ion-trap instrument is investigated. If all ions observed in conventional EI mass spectra are detected, ion/molecule reactions are seen to occur leading to formation of protonated molecules and adduct ions such as 2M+· and [2M + H]+. The keto-to-enol-like isomerization of the molecular M+· ion seems to favour proton transfer to neutral M species and a “self chemical ionization” ion is observed with corresponding fragment ions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1594-1598 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The classical n-butylbenzene model is used to estimate the qualitative variation of the precursor ion internal energy by the resonant excitation method in an ion-trap mass spectrometer. The kinetic energy thermalization process is confirmed by insertion of a cooling time (≤10ms under our conditions). An initial internal energy relaxation process due to collisions between the molecular ion and neutral species of n-butylbenzene is proposed. The larger amount of internal energy deposited in ions as the helium pressure is increased can be explained in terms of the number of collisions between the molecular ion and helium atoms, the competition between ion dissociation and ion ejection, the rate constant of dissociation and the secular axial frequency resolution of the isolated ions. Increased analyte pressure does not accelerate the ion relaxation process, probably due to the space charge effects. In summary, variation of helium pressure and cooling time permit optimization of ion internal energy deposition leading to enhanced sensitivity in MS/MS experiments.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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