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  • Analytical Chemistry and Spectroscopy  (5)
  • 2000-2004
  • 1985-1989  (5)
  • 1940-1944
  • 1
    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.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 16 (1988), S. 409-413 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gas chromatography/electron capture negative ion mass spectrometry of eicosanoids, as pentafluorobenzyl (PFB) ester, methyl oxime (where applicable), trimethylsilyl (TMS) ether derivatives, is reported using a double-focusing instrument of trisector configuration. Sub-picogram detection limits were observed for prostaglandins E1, E2 and F2α during selected ion monitoring (SIM) of [M — PFB]- ions. Selected reaction monitoring (SRM) of [M — PFB]- → [M — PFB — TMSOH]-, occurring in the first field-free region, was of modest sensitivity, reflecting the stability of the [M - PFB]- ions. The leukotriene B4 (LTB4) derivative was successfully analyzed by SIM at the low-picogram level. In this instance, the fragmentation [M — PFB]- →[M — PFB — TMSOH] occurred in high yield in the first field-free region. The advantageous improvement in selectivity of detection that may be achieved with SRM was evident during the analysis of a serum extract for LTB4.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 26 (1988), S. 214-223 
    ISSN: 0749-1581
    Keywords: RELAY 2D NMR ; 1H NMR ; 2D NMR Steroids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relayed coherence transfer (RELAY) two-dimensional NMR spectroscopy was demonstrated to be an effective technique for overcoming the problem of overlapping multiplets in the analysis of the 1H NMR spectra of steroids. Cross-sections through appropriate proton resonances resulted in resolved spectra of the spin systems for each of the saturated rings of the estrogenic hormones 17β- and 17α-estradiol. During RELAY experiments with a fixed delay time of 0.042 s it was possible to observe RELAY cross-peaks between H-11α and 18-CH3 which resulted from magnetization transfer via long-range coupling between 18-CH3 and H-12α. The difference in stereochemistry at C-17 of these estradiol epimers allowed an examination of the effect of substituent configuration on the RELAY cross-peak intensity in order to determine the ability of the RELAY method to provide qualitative structural information.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0749-1581
    Keywords: 1H ; 13C NMR 2D NMR ; C-Glycopyranosides ; C-Glycofuranosides ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C-Glycopyranosides and C-glycofuranosides were identified using 13C and 1H chemical shift and coupling constant data. Full assignments for all α- and β-anomers were made possible by recourse to carbon-proton chemical shift correlation spectroscopy. Greater steric shielding effects were observed on the carbon atoms in cis-1,2-substituted compounds compared with their trans counterparts. Consistent proton chemical shift differences were also noted in that the anomeric protons resonate at lower field in all cis-1,2-isomers.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 26 (1988), S. 1058-1061 
    ISSN: 0749-1581
    Keywords: Two-dimensional NMR ; Artifacts ; BIRD pulses ; Coherence transfer ; Methylene groups ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When the proton-proton decoupled heteronuclear two-dimensional chemical shift correlation experiment is applied to a molecule containing methylene groups, the spectra show not only the expected signals at the two proton chemical shifts, but also a strong artifact. This artifact appears at the average of the two proton chemical shifts, and arises from coherence transfer between the two protons caused by the BIRD pulse. It is not caused by strong coupling between the protons, and so may appear in any spectrum. The dependence of this artifact on experimental conditions was analysed, and is illustrated with results obtained on the methylene groups from the cyclophane ring in N6′,N9-octamethylenepurinecyclophane.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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