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  • Analytical Chemistry and Spectroscopy  (704)
  • 1985-1989  (680)
  • 1965-1969  (24)
  • 1940-1944
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  • 1
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The data obtained with 252Cf plasma desorption (PD) and fast atom bombardment mass spectrometry of eight tri-, tetra- and pentapeptides were compared. Good spectra were obtained with 1-10 nmol of peptide. In both techniques molecular weight information was obtained. The PD mass spectra are often dominated by the cationized molecular ions in contrast to the fast atom bombardment (FAB) mass spectra, where cationization is rarely observed. Amino acid content is reflected in the immonium ions equally well in both techniques. The fragmentation patterns observed with the two techniques are almost identical. However, practical sequencing of peptides based on either FAB or PD mass spectrometry of underivatized peptides alone is difficult. This is due to the unpredictable and sometimes absent cleavage yield at certain peptide bonds. Another difficulty is the many simultaneous fragmentation pathways. However, for many peptides enough information is present to allow sequence determination for at least a major part of the molecule.
    Additional Material: 2 Ill.
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  • 2
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The urines of children with neonatal adrenoleukodystrophy and Zellweger syndrome contained an excess of unusual even- and odd-numbered dicarboxylic acids with a chain length of from 5 to 15 carbon atoms, as well as 2-hydroxy-compounds, including 2-hydroxy-isocaproate, 2-hydroxy-glutarate and 2-hydroxy-sebacate. The latter product, not previously found in metabolic diseases, appears as an additional useful marker of these peroxisomal disorders.
    Additional Material: 3 Ill.
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  • 3
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During sequence determination of a structural protein from the cuticle of the migratory locust, Locusta migratoria, a discrepancy was found between the molecular weight calculated from the sequence data (15 323) and that estimated by SDS-gel electrophoresis (21 600). The protein contains several repeated sequences, and the discrepancy might indicate that part of the sequence was missing or that the protein contained a large prosthetic group. The molecular weight of the protein was determined by 127I-plasma desorption mass spectrometry to be 15 329±50 which confirms the sequence data and shows the molecular weight determination based on SDS-electrophoresis to be too high.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 291-293 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the process of developing a high-sensitivity negative chemical ionization gas chromatographic/mass spectrometric assay for brain and cerebrospinal fluid (CSF) levels of quinolinic acid (QUIN, 2,3-pyridine dicarboxylic acid), (18O4)QUIN was prepared. Its properties as an internal standard were compared with those of the structural isomer 2,4-pyridine decarboxylic acid (2,4-PDC) previously used by others. All oxygen atoms in QUIN were labeled by heating in 3N HCl/(18O)water for 48 h at 80°C. Back-exchange of (18O4)QUIN was prevented during derivatization to an electron-capturing dihexafluoropropanol ester by using trifluoroacetylimidazole as catalyst instead of perfluroacyl anhydrides. When mixtures of QUIN and (18O4)QUIN and/or 2,4-PDC were followed through a procedure to isolate and quantify brain and CSF QUIN, the variability in the ratio of QUIN:2,4-PDC was greater than for QUIN:(18O)QUIN. We conclude that (18O)QUIN is the preferred internal standard in gas chromatographic/mass spectrometric quantification of brain and CSF QUIN, and that (18O)-labeled carboxylic acids may be esterified effectively without back-exchange using acylimidazole reagents.
    Additional Material: 1 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1988), S. 305-310 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polycyclic peptide antibiotic, Nisin, has been analysed by plasma desorption mass spectrometry using two different sample preparation techniques and two versions of the commercial plasma desorption mass spectrometer, and a prototype with high resolving power. The spectra obtained allow identification of a major component and two minor analogues. Extensive fragmentation is observed in samples prepared by the electrospray technique, whereas only ions indicating the molecular weight are produced when the sample is adsorbed on nitrocellulose.
    Additional Material: 5 Ill.
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  • 6
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using fast atom bombardment (FAB) ionization combined with tandem mass spectrometry (MS/MS), the identity of arsenobetaine (AB) in extracts of sole, haddock, lobster and shrimp was unequivocally confirmed. Evidence was also presented for the presence of arsenocholine (AC) in the shrimp extract. Confirmation was obtained by comparing the collision-induced dissociation (CID) daughter ion and parent ion spectra of major ions in the FAB spectra from these extracts with those from the authentic standards.
    Additional Material: 10 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 18 (1989), S. 48-56 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metabolism of cyclosporin A (CsA) was studied in a model of isolated and perfused rabbit liver, and in man. After diethyl ether extraction, CsA metabolites were separated and successfully purified by a combination of two highperformance liquid chromatographic (HPLC) procedures. A normal-phase HPLC methodology was used to separate most of the metabolites, and further separation and purification were optimized with a reversed-phase HPLC method. 27 different CsA metabolites were separated, collected, and characterized by fast atom bombardment mass spectrometry. In addition to several metabolites already described (OL-1, OL-17, OL-18 and OL-21), new compounds (of original molecular weights 1236, 1222 and 1174, and numerous structural isomers of previously reported molecular weights) were isolated from rabbit and human bile. Mass spectral analysis of two of these new metabolites strongly suggests vicinal dihydrodiol (mol. wt 1236) and N-demethylated vicinal dihydrodiol (mol. wt 1222) structures. These two new metabolites most probably derive from an epoxide as a preliminary intermediate.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 18 (1989), S. 301-307 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra of many rifamycins cannot be obtained by electron ionization (EI) owing to their thermal decomposition. When a laser beam is used to vaporize the sample through an optic fibre inserted in a hollow probe which reaches the sample cup, decomposition is minimized and the EI spectra show abundant molecular ions and fragments of structurally high diagnostic value. These ionic species are easily observed owing to the lack of chemical noise often present in soft ionization methods, such as direct liquid chemical ionization and fast atom bombardment.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Positive and negative plasma desorption (PD) mass spectra of the di-deoxyribonucleoside monophosphate d(TpT) and of its biologically relevant ultraviolet-induced intramolecular photodimers are examined and discussed. The photodimers which were analysed by PD mass spectrometry include the cis-syn and trans-syn cyclobutyl isomers d(T[p]T), the pyrimidine-pyrimidone photoadduct (6-4)d(TpT) and its Dewar valence isomer. Molecular ions, quasi-molecular ions and several fragment ions are observed in all cases. It is shown that, despite the absence of mass differences between these dinucleoside monophosphates, the fragmentation pattern differs significantly between the two main classes: cyclobutane dimers and (6-4) adducts. PD mass spectrometry can therefore be envisaged for characterizing their formation within short DNA fragments.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 14 (1987), S. 689-697 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the identification of intact underivatized drug conjugates, the mass spectrometric technique of choice is fast atom bombardment (FAB); the combined use of both positive and negative ion FAB usually provides information on the molecular mass and nature of conjugates under study, while the number of exchangeable hydrogen atoms can be determined using trideuterated glycerol as the FAB-matrix. Electron impact and desorption chemical ionization spectra can be used to study the aglycone part of the conjugated metabolites. With this approach metabolites conjugated with glucuronic acid, sulphuric acid and amino acids have been identified. The identification was supported by analysis of reference compounds, prepared by chemical synthesis. The examples given are selected from current metabolism studies on drug candidates in development within Organon's research.
    Additional Material: 9 Ill.
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