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  • Mass spectrometry  (3)
  • Gas chromatography/mass spectrometry  (2)
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Biology and fertility of soils 20 (1995), S. 174-184 
    ISSN: 1432-0789
    Schlagwort(e): Agriculture ; Flash pyrolysis ; Gas chromatography/mass spectrometry ; Heterocyclics ; Mineral soils ; Organic nitrogen ; Unknown N
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Curie-point pyrolysis-gas chromatography mass spectrometry with N-selective detection was used to characterize the structure of organic N compounds in four mineral soils. The technique was found suitable for the fast, sensitive, and highly specific identification of N-containing pyrolysis products from whole soils with total N contents between 0.08 and 0.46%. In order to optimize the methodology, one agricultural soil was pyrolyzed at final temperatures of 573, 773, and 973 K. Almost no chemical alterations to identifiable pyrolysis products were observed when the final pyrolysis temperature was increased from 573 to 973 K. More than 50 N-containing pyrolysis products were identified, and were divided into compound classes chracterized by specific molecular-chemical structures. These included pyrroles, imidazoles, pyrazoles, pyridines, pyrimidines, pyrazines, indoles, quinolines, N derivatives of benzene, alkyl nitriles, and aliphatic amines. Three additional soil samples different in origin and N content were analyzed at 773 K and each showed a specific thermosensitive N-selective chromatogram. Many N-containing pyrolysis products were identified in all samples, which indicated general qualitative regularities in the thermal release of N-containing pyrolysis products from the four soils. In the pyrolyzates of the investigated soils a number of compounds were identified, which is usually not detectable in pyrolysis-gas chromatography spectrometry analyses with N-selective detection of plants and microorganisms. Among these were N derivatives of benzene and long-chain alkyl nitriles, which appear to be soil-specific and suggest significant transformations of organic N in soils. Thus, our results contribute to a better understanding of the molecular-chemical structure of unknown N.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Biology and fertility of soils 26 (1997), S. 1-15 
    ISSN: 1432-0789
    Schlagwort(e): Key words Analytical pyrolysis ; Humic substances ; Heterocyclic nitrogen ; 15N NMR ; Mass spectrometry ; Soil organic matter ; Model structure ; Unidentified nitrogen
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract 1. From the data presented herein it is possible to deduce the following distribution of total N in humic substances and soils: proteinaceous materials (proteins, peptides, and amino acids) – ca. 40%; amino sugars – 5–6%; heterocyclic N compounds (including purines and pyrimidines) – ca. 35%; NH3–19%; approximately 1/4 of the NH3 is fixed NH4 +. Thus, proteinaceous materials and heterocyclics appear to be major soil N components. 2. Natural 15N abundance levels in soils and humic materials are so low that direct analysis by 15N NMR is very difficult or impossible. To overcome this difficulty, the soil or humic material is incubated with 15N-enriched fertilizer. Even incubation in the laboratory for up to 630 days does not produce the same types of 15N compounds that are formed in soils and humic materials over hundreds or thousands of years. For example, very few 15N-labelled heterocyclics are detected by 15N NMR. Does this mean that heterocyclics are not present? Or are the heterocyclics that are present not labelled under these experimental conditions and therefore not detected by the 15N NMR spectrometer ? Another possibility is that a large number of N heterocyclics occur in soils, but each type occurs in very low concentrations. Until the sensitivity is improved, 15N NMR will not provide results that can be compared with data obtained from the same soil and humic material samples by chemical methods and mass spectroscopy. 3. What is most important with respect to agricultural is that all major N forms in soils are available to organisms and are sources of NH3 or NH4 + for plant roots and microbes. Naturally, some of the NH3 will enter the N cycle. 4. From chemical and pyrolysis-mass spectrometric analyses it appears that N heterocylics are significant components of the SOM, rather than degradation products of other molecules due to pyrolysis. The arguments in favor of N heterocyclics as genuine SOM components are the following: a) Some N-heterocyclics originate from biological precursors of SOM, such as proteinaceous materials, carbohydrates, chlorophyll, nucleic acids, and alkaloids, which enter the soil system as plant residues or remains of animals. b) In aquatic humic substances and dissolved organic matter (DOM) at considerably lower pyrolysis temperatures (200 to 300°C), free and substituted N-heterocyclics such as pyrroles, pyrrolidines, pyridines, pyranes, and pyrazoles, have been identified by analytical pyrolysis (Schulten et al 1997b). c) Their presence in humic substances and soils was also detected without pyrolysis by gel chromatography – GC/MS after reductive acetylation (Schnitzer and Spiteller 1986), by X-ray photoelectron spectroscopy (Patience et al. 1992), and also by spectroscopic, chromatographic, chemical, and isotopic methods (Ikan et al. 1992). 5. While we can see light at the end of the tunnel as far as soil-N is concerned, further research is needed to identify additional N-containing compounds such as N- heterocyclics, to determine whether these are present in the soil or humic materials in the form in which they were identified or whether they originate from more complex structures. If the latter is correct, then we need to isolate these complex N-molecules and attempt to identify them.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Biology and fertility of soils 24 (1997), S. 249-254 
    ISSN: 1432-0789
    Schlagwort(e): Key words Acid hydrolysis ; Agriculture ; Analytical pyrolysis ; Field ionization mass spectrometry ; Gas chromatography/mass spectrometry ; Heterocyclics ; Mineral soils ; Unknown nitrogen
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Curie-point pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and in-source pyrolysis-field ionization mass spectrometry (Py-FIMS) were applied for the first time to the structural characterization of organic nitrogen in hydrolyzates and hydrolysis residues resulting from the classical 6M HCl hydrolysis of mineral soils. Two well-described soils of widely different origin (i.e., a Gleysol Ah and a Podzol Bh) were investigated. Py-GC/MS was performed using a nitrogen-selective detector to detect and identify N-containing pyrolysis in the hydrolyzate (e.g., pyrazole and/or imidazole, N,N-dimethylmethanamine, benzenacetonitrile, propane- and propenenitriles) and the hydrolysis residue (e.g., pyrroles, pyridines, indoles, N-derivatives of benzene, benzothiazol, and long-chain aliphatic nitriles). Moreover, temperature-resolved Py-FIMS allowed us to record the thermal evolution of the N-containing compounds during pyrolysis. These were characterized by a particularly high thermostability compared to their thermal release from whole soils. The combination of pyrolysis with mass spectrometric methods permitted analyses of the identities and thermal stabilities of complex nitrogen compounds in hydrolysis residues of whole soils, which cannot be done by wet-chemical methods. Pyrolysis-methylation GC/MS with tetramethyl-ammonium hydroxide (TMAH) as methylating agent enabled the identification of N,N-dimethylbenzenamine and so confirmed the identification of benzeneamine by Py-GC/MS in nonmethylated hydrolysis residues. The described N-derivatives of benzene and long-chain nitriles are usually not detectable by pyrolysis-mass spectrometry of plants and microorganisms. These compounds are characteristic of soils, terrestrial humic substances and hydrolysis residues and seem to be specific, stable transformation products of soil nitrogen.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 14 (1975), S. 403-415 
    ISSN: 0570-0833
    Schlagwort(e): Mass spectrometry ; Analytical methods ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Field desorption (FD) enables mass-spectrometric investigation of large organic molecules without their vaporization. The present state of our theoretical understanding of the ionization of these molecules in the adsorbed state on organic emitters is described. The special problems of the technique and prospective developments in the apparatus for future analytical problems are outlined. The present progress report concentrates on analytical studies of biochemical model compounds and degradation products from environmental chemicals and drugs. The method is particularly suitable for the detection and identification of submicrogram quantities of underivatized polar substances present in complex mixtures or pre-purified extracts from biological materials.
    Zusätzliches Material: 19 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 17 (1978), S. 221-238 
    ISSN: 0570-0833
    Schlagwort(e): Mass spectrometry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The current state of quantitative analysis with the mass spectrometer in biochemistry and medicine is reviewed. The basic principles of mass spectrometry, the latter's combination with chromatography, the development of sensitive, exact, and in particular specific mass-spectrometric methods of detection, and the principle of dilution with stable isotopes are illustrated by examples. The most important fields of application are: the pharmacokinetics of drugs and active metabolites, investigation of metabolic pathways, supporting of medical diagnoses and enhancement of their specificity, and finally checking the quality of simpler quantitative processes in clinical chemistry.
    Zusätzliches Material: 19 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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