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  • Analytical Chemistry and Spectroscopy  (39)
  • Earth Resources and Remote Sensing  (19)
  • Astrophysics  (9)
  • Astronomy  (6)
  • 1
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The determination of serum cortisol by thermospray liquid chromatography/mass spectrometry (LC/MS) has been assessed. The method incorporates stable isotope dilution and innumoadsorption extraction. [M + H]+ ions are monitored during LC/MS. The within-assay reproducibility is satisfactory (coefficient of variation 7% at a concentration of 190 ng ml-1), though inferior to that achieved with the (more lengthy) procedure of gas chromatography/mass spectrometry (GC/MS). Satisfactory agreement between LC/MS (y) and GC/MS (x) data was observed (y = 0.934x + 12.4 ng ml-1; r = 0.968; n = 14). It is concluded that the generation of precise reference data for the assessment of routine cortisol assays is at present better achieved by GC/MS. LC/MS, however, provides satisfactory quantitative data via a more simple and rapid method.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 99-104 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydroepiandrosterone sulphate (DHAS) has been quantified in human blood serum by fast atom bombardment (FAB)/tandem mass spectrometry of immunoadsorption extracts. FAB of DHAS yielded abundant ions corresponding to the intact steroid sulphate; these were selected by a double-focusing mass spectrometer prior to collisionally activated decomposition in a quadrupole collision cell and mass analysis by a quadrupole mass filter. [HSO4]- (m/z 97) was the sole prominent daughter ion. For quantitative analyses the quadrupole mass filter was set to transmit m/z 97 and a narrow-range magnet scan yielded a spectrum of parents, including m/z 367 and 369, corresponding to DHAS and the (2H2)-analogue (used as internal standard), respectively. Serum concentrations by this procedure were in good agreement with data obtained by gas chromatographic/mass spectrometric analyses of DHA heptafluorobutyrate, formed by direct derivatization of the steroid sulphate.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 18 (1989), S. 439-444 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure is described for the quantitative determination of platelet activating factor (PAF) using stable isotope dilution and fast atom bombardment/tandem mass spectrometry. Low-energy collisional activation of the [M + H]+ ion of PAF yields a single daughter ion of m/z 184, characteristic of phosphocholine derivatives. For precise and accurate quantification the internal standard is (2H3)acetyl-hexadecyl PAF, which yields an analogous daughter ion of m/z 185. Quantitative analyses are based on limited mass-range parent ion scanning with transmission of daughters of m/z 184 and 185 during alternate scans; all scans are accumulated into a single data file to facilitate determination of the analyte/internal standard response ratio. Analysis of authentic hexadecyl PAF indicates a low-picogram detection limit. The method has been applied to the determination of PAF in preparations of human neutrophils stimulated by addition of a calcium ionophore. Concentrations of PAF of 7-17 ng/106 cells were observed, in keeping with earlier reports. The method has been validated by standard addition and dilution experiments. Comparison of data obtained by the new procedure and those obtained by a method involving gas chromatography/electron capture mass spectromery of dephosphorylated and derivatized PAF showed excellent agreement.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 183-184 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 615-621 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The collisionally activated decomposition of [M + H]+ ions, generated by fast atom bombardment (FAB) of glutathione conjugates, has been studied by tandem mass spectrometry (MS/MS) using hybrid sector/quadrupole instruments. Abundant fragments of diagnostic utility were present in the daughter ion spectra. Common fragmentation modes were observed but their relative importance was strongly dependent on the nature of the conjugated species. As an example of a general approach to the characterization of glutathione conjugates in biological samples, the acetaminophen-glutathione conjugate was identified in rat bile, following coadministration of (2H0)- and (2H3)acetaminophen, using the experimental sequence: (i) conventional FAB mass spectrometric analysis, (ii) MS/MS using constant neutral loss (129 u) scanning to identify parent ions corresponding to glutathione conjugates, (iii) MS/MS to yield daughter ion spectra of parents so identified and corresponding to (2H0)- and (2H3)-labeled conjugates.
    Additional Material: 3 Ill.
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  • 6
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The collision-induced decomposition (CID) of ions in the collision cell of a four-sector tandem mass spectrometer (EBEB) was studied as a function of cell potential and collision gas over the mass range 246-1847. When the cell is at a potential of 2 kV or greater above earth, the loss of light ions by scattering is negligible and the detection sensitivity for light ions increases owing to their being reaccelerated on leaving the cell. The CID spectra given by helium and argon are very similar for ions derived from samples of m/z ≤ 1000 but at higher masses argon is the more efficient collision gas.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 28 (1993), S. 316-320 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The He I photoelectron spectra of 2-, 3- and 4-methoxypyridine are reported and interpreted in terms of a composite-molecule model and ΔSCF/MP ionization energies. For pyridine, this ab initio method correctly locates the nitrogen lone-pair molecular orbital with respect to experiment and shows quantitatively the importance of incorporating both correlation and relaxation effects. Comparison of experimental and ab initio ionization energies of the methoxypyridines with the semi-empirical HAM/3 method further substantiates the utility of HAM/3 for the interpretation of photoelectron spectra.
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  • 8
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Frangmentation yields during high-energy collisionally activated decomposition (CAD) tandem mass spectrometie experiments are often low, due in part to the short time-period available for the fragmentations. Consequently, attempts at multi-stage mass spectrometry undeer high-energy CAD conditions can give unsatisfactory result when a conventional point detector is used. Arry detection dramatically improves the detection of ion currents of low abundance; we therefore incorporated arry detection in a variety of sequential product-ion ‘scanning’ experiments, including MS3 and MS4, using a BEBE instrument. The corresponding experiments were previously established on a BEqQ hybrid instrument. where the final stage of decomposition occurred under low-energy CAD conditions. The results from the hybrid were used as a basis of comparison for the results under high-energy CAD with array detection. On the BEBE instrument, the use of the array greatly enhanced the signal-to background ratio for second-and third-generation product-ion spectra, as compared to the use of the point detector on the instrument in several instances, the use of the array was criticaL to the success of the experiment on the four-sector instrument. For the peptides analyzed, the fragmentation patterns observed in the sequential product spectra were similar on the four-sector instrument and on the hybrid instrument, although the relative abundances differed between the high-and low energy CAD regimes. Reaction-intermediate scanning, involving two sequential decomposition step occurring on the microsecond high energy time scale, has also been implemented on the BEBE instrument. A New mode of reaction-intermediate scanning has also been implemented on the BEqQ hybrid instrument, permitting it to access sequential fragmentation when both occur under high-energy CAD conditions.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 6 (1992), S. 658-662 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: We have examined the hypothesis that structural features which predispose to localization of charge at a strongly favored site are not conducive to the low-energy fragmentation of peptide ions via a multiplicity of pathways. Consistent with this proposal, it is demonstrated that the formation of N- or C-terminal pre-charged derivatives is detrimenal to the formation of sequence-specific product ions following low-energy collisional activation. Protonation of pre-charged derivatives (yielding doubly charged ions) restores favorable fragmentation properties; the effect is attributed to the fragmentation-directing properties of the proton whih may occupy one of several sites. Similarly, a doubly protonated peptide which incorporates a C-terminal arginine residue as a single strongly favored site of protonation exhibits favored low-energy fragmentations attributable to locaton of he second proton at one of several sites remote from the C-terminus.
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  • 10
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Fast-atom bombardment mass spectrometry of a synthetic renin substrate decapeptide (Pro-His-Pro-Phe-His-Leu-Val-Ile-His-D-Lys) indicated the presence of several of side-products, including a component 12 Da higher in mass. Low-energy collisionally activated decomposition analyses were performed using a hybrid tanden, instrument and demonstrated that the heavier side product had two components, in which the structural modification was either at the N- or the C-terminus. Additional analyses of the N-acetyl derivative indicated that for each component the strucutrual modification blcoked a site of N-acetylation. It is suggested that the formation of these side products is attributable to the generation of formaldehyde, during removal of the histidine protecting group (benzyloxymethyl), which reacts with the N-terminus of the peptide to give an imidazolidinone structure or with the D-lysine ε-amine group to yield an imine. While the precise genesis of the side-products remains speculative, it is clear that the combined strategy of derivatization and tandem mass spectrometry has allowed structural conclusions concerning individual components of an isobaric mixture.
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