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  • Chemistry  (7)
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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 18 (1989), S. 581-591 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser microprobe mass spectrometry has been applied to a variety of organic polyfunctional molecules, covering a wide range of polarity and mass spectrometric behaviour. The technique apparently combines desorption under relatively soft conditions with extensive fragmentation and hence allows much structural information from intactly released thermolabiles to be obtained. The mass spectra appear unfamiliar in comparison to conventional techniques. Interpretation is attempted in a purely empirical way by means of the evidence from our database and tentative hypotheses to rationalize the desorption and ionization by laser microbeam irradiation of organic solids. Selected examples are presented to illustrate the potential and limitations of the method in the field of biomolecules, such as pyridoxine and pyridoxal phosphate, nucleosides, nucleotides and related analogues, drugs and the corresponding N-oxides.
    Additional Material: 5 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 objective of this study was exploration of the potential, offered by the laser microprobe mass spectrometer (LAMMA), for the in situ localization of organic targets in embedded tissues by means of structurally relevant ions. A series of model systems was designed to evaluate stepwise the analytical problems involved. A preliminary screening pointed to the position of the target in comparison to the actual sample surface as a determining parameter. Refined simulations were carried out with sandwich samples, consisting of an epon carrier (thickness 1 μm), coated with microcrystalline targets and covered with a layer between 5 and 50 nm of different materials (epon, carbon, formvar). In addition to a stimulated conversion of molecular into fragment ions, the presence of a barrier leads to a drastic loss of sensitivity (20-50 x) and unacceptable degradation of the mass spectrometric quality (resolution, calibration).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 16 (1988), S. 121-129 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser microprobe mass analysis (LAMMA) was used for the structural characterization of polyfunctional drugs and their oxygenated metabolites, in particular the N-oxides. The spectra usually yield the molecular weight as well as intense fragments. The structural information is characteristically distributed between the positive and negative ions. To rationalize the unfamiliar fragmentation, tentative pathways are introduced. Key elements are the formation of odd-electron molecular (and fragment) ions, the correlation between cations and anions, as well as the three-dimensional representation of structures. The combination of mild desorption and abundant fragmentation makes LAMMA a valuable tool in the study of N-oxides.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1980), S. 473-483 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the last decade, a considerable amount of information has been gathered on the organic composition of aerosols, mostly sampled by Hi-Vol filtration, and analysed by gas chromatography or gas chromatography mass spectrometry. From our research, it appears that care should be taken in the use of such data for the evaluation of health hazards, resulting from air pollution. The following facts must be considered.(1) The conventional Hi- Vol filtration sampling technique can be subject to several sampling artifacts, such as volatilization from and chemical reaction on the filter. Indeed, a series of compounds of intermediate volatility has been shown to evaporate from particles on the filter, when exposed to large air volumes. Low molecular weight compounds are predominant in the gas phase, and high molecular weight ones in the particulate phase. Furthermore, some pollutants on collected particles can react with molecular or radical species, present in the atmosphere: e.g. the carcinogen benzo (a)pyrene can be degraded very rapidly by traces of ozone to highly polar compounds. (2) Besides pollutants of anthropogenic origin, natural sources may also contribute to the aerosol burden. Thus, the presence of the higher odd carbon numbered n-alkanes reflects the contribution from vegetation (plant waxes). The possible synergistic activity of these compounds in combination with carcinogens, justifies the monitoring of these contaminants in aerosols. (3) Since the retention of particles in the respiratory tract strongly depends on particle size, measurements of total pollutant concentrations have to be supplemented with particle size distribution data. The analysis of several size fractionated samples, taken at suburban as well as at remote rural and sea shore sites, allows the evaluation of the dilution of particulate organics and of the differences in particle size distributions in the background areas. Most pollutants are almost exclusively distributed over the respirable particle size range (below 3 μm) and any observed distribution shifts remain within this range. In conclusion, a realistic estimate is presented of the fractions deposited in and extracted by the tissues of the respiratory tract. These are directly responsible for the health hazards, associated with breathing aerosol particles. It follows that a nearly constant fraction of a given pollutant, enters the bloodstream, irrespective of the sampling site, and thus health hazards remain closely related to the total concentration levels.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 323-331 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Laser microprobe mass spectrometry (LMMS) employs focused laser-beam irradiation of solids and subsequent mass analysis of the ions produced. The technique is suitable for the local analysis of inorganic and organic constituents with a spatial resolution in the micrometer range. The Fourier transform mass spectrometer (FTMS) is an analyser of choice for LMMS because high mass resolution and accurate mass determination can be routinely achieved at adequate sensitivity. This paper describes the first LMMS instrument using FTMS with an external ion source. The design considerations and the experimental performance are described with respect to such analytical parameters as spatial resolution and sensitivity. A comparison between time-of-flight mass spectrometry and IT-LMMS for diagnostic analysis of organic molecules is interpreted in terms of the ion formation processes. Finally, the analysis of a selected integrated circuit evidences the feasibility of local analysis with a spatial resolution of 5 μm.
    Additional Material: 10 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: Laser microprobe mass spectrometry (LMMS) has been applied systematically to a variety of organic polyfunctional molecules, covering a wide range of structures and polarities. The microprobe generally offers a combination of desorption under relatively mild conditions with abundant fragmentation. We attempted an empirical approach by tentative hypotheses about desorption and ionization in LMMS to consistently rationalize the detected fragments. The complementary nature of structural data, carried by positive and negative ions, is characteristic for LMMS results of non-ionic compounds. The analysis of salts represents, traditionally, an ultimate test case for soft methods in organic mass spectrometry. Hence, by a selected series of compounds, we have tried to assess to which extent the presence of preformed ions becomes an asset for LMMS analysis and affects the amount, the accessibility or the distribution of organic information between positive and negative fragments.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser microprobe mass spectrometry (LMMS) has been used to systematically study polyfunctional molecules, covering a wide range of structure and polarity. The knowledge about the mechanisms actually involved for desorption and ionization (DI) of organics by laser microbeam irradiation of solid samples at high-power density is rather limited. Therefore we have elaborated a set of tentative hypotheses about DI in LMMS, permitting consistent rationalization of detected signals. The technique apparently combines desorption under mild conditions, shown by the release of intact thermolabiles, with extensive fragmentation. Structural data are typically distributed between cations and anions. Interpretation of negative-ion detection mode mass spectra often represents intricate problems, partly due to the lack of sustaining background information from conventional mass spectrometry. Selected examples are presented to illustrate the occurrence of electron capture ionization, the role of heteroatoms in the formation of negative ions and the tendency to undergo complex skeletal rearrangements. Although LMMS was originally aimed at microprobe applications, it has been found to be a valuable tool in organic mass spectrometry.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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