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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 26 (1997), S. 1-15 
    ISSN: 1432-0789
    Keywords: Key words Analytical pyrolysis ; Humic substances ; Heterocyclic nitrogen ; 15N NMR ; Mass spectrometry ; Soil organic matter ; Model structure ; Unidentified nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 155 (1987), S. 1-20 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der thermische Abbau von aromatischen polyamiden wie kelvar (Poly-1,4&(phenylen-terephthalamid)) und Nomex (Poly&(1,3-phenylen-isophthalamid)) wurde mit Pyrolyse-Feldionisation-Massensperktrometrie (Py-FIMS) und Pyrolyse-Gaschro-matographie (Py-GC) untersucht. Bei den Messungen mit Py-FIMS wurden die Proben in der Ionenquelle eines doppel-fokussierenden massensperktrometers im Temperaturbereich von 50°C bis 750°C bei einer Heizrate von 1,2° “C/s pyrolysiert”. Zahlreiche gemeinsame und charakteristische Abbauprodukte der beiden Proben, bzw. der entsprechenden para- und meta-Isomeren, wurden im Massenbereich bis m/z 500 gefunden, allerdings mit erheblichen Intensitätsunterschieden. Die Hauptprodukte wurden durch homolytische Reaktionen sowie durch Hydrolyse gebildet. Andererseits wurden die bei 720° gebildeten thermischen Abbauprodukte gaschromatographisch mit einer gebundenen Silicagel-Säule getrennt. Der Nachweis erfolgte sowohl durch einen Flammenionisations-Detektor als auch durch Elektronen-stoß-(EI)-Massenspektrometrie. Obwohl viele der Abbauprodukte mit denen der beiden Py-FIMS Messungen gefundenen übereinstimmten, setzten sich erstere vorwiegend aus solchen Produkten zusammen, welche durch radikalische, homolytische Reaktionen gebildet werden. Die Unterschiede zwischen der Zusammensetzung der thermischen Abbauprodukte der beiden Proben waren allgemein mit Py-GC erheblich geringer, als bei Py-FIMS beobachtet wurde.
    Notes: The thermal degradation of aromatic polyamides such as poly&(1,4-phenyleneterephthalamide) (Kevlar) and poly&(1, 3-phenylene-isophthalamide) (Nomex) was studied by pyrolysis-field ionization mass spectrometry (Py-FIMS) and pyrolysis-gas chromatography (Py-GC). In Py-FIMS, the thermal degradation products were recorded which were formed in the ion source of a double focusing mass spectrometer. Usually a temperature range from 50 to 750°C and a heating rate of 1.2°C/s were employed. Various common and characteristic products for the two samples, respectively the corresponding para- or meta-isomers, were observed up to m/z 500 with significant differences in intensity. The main products observed were produced by both radical homolytic and hydrolytic decompositions.On the other hand, in flash Py-GC the instantaneous thermal degradation products at 720°C were gas-chromatographically separated by a fused-silica capillary column and detected both by a flame ionization detector and a mass spectrometer with electron ionization (EI). Although many of the degradation products were identical with those observed by Py-FIMS, the former almost entirely consisted of the fragments formed through radical homolytic degradation. In general, the differences between the samples with Py-GC were much less than those observed in Py-FIMS.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 184 (1991), S. 133-146 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(acrylnitril), Butadien-Acrylnitril-Copolymeres und Styrol-Acrylnitril-Copolymere mit Acrylnitrilgehalten zwischen 8 und 50 mol-% wurden mit der Pyrolyse-Feldionisation-Massenspektrometrie untersucht. Im registrierten Massenbereich von 50 bis 1200 g/mol wurden Molekülionen von thermisch gebildeten Oligomeren mit bis zu 16 monomeren Untereinheiten registriert. Im Spektrum des Butadien-Acrylnitril-Copolymeren stehen die relativen Häufigkeiten der Signale von Oligomeren mit der gleichen Gesamtanzahl monomerer Untereinheiten in guter Übereinstimmung mit einer zufälligen Verteilung dieser Untereinheiten im Polymeren. Im Gegensatz hierzu ergaben sich aus den relativen Häufigkeiten der Signale in den Spektren sämtlicher Styrol-Acrylnitril-Copolymerer zu hohe Acrylnitrilgehalte. Andererseits zeigten die Spektren, daß Styrol-Acrylnitril-Sequenzen wesentlich häufiger auftreten als es einer Zufallsverteilung entspricht, während die relativen Häufigkeiten der Signale von Oligomeren mit Styrol-Styrol- oder Acrylnitril-Acrylnitril-Sequenzen wesentlich geringer sind als für die zufällige Verteilung der monomeren Untereinheiten zu erwarten wäre. Diese Ergebnisse können mit einer erhöhten Stabilität von Styrol-Acrylnitril-Diaden erklärt werden.
    Notes: Poly(acrylonitrile), butadiene-acrylonitrile copolymer, and styrene-acrylonitrile copolymers with acrylonitrile contents between 8 and 50 mol-% have been investigated by pyrolysis-field ionization mass spectrometry. Molecular ions of thermally-formed oligomers containing up to 16 monomeric subunits were recorded in the mass range 50 to 1200 g/mol. With the butadiene-acrylonitrile copolymer, the relative abundances of signals due to oligomers with the same total number of monomeric subunits is close to the random distribution of these subunits in the polymers. In contrast, with the styrene-acrylonitrile copolymers the acrylonitrile contents indicated by relative abundances are too high with all samples. On the other hand, the mass spectra confirm that styrene-acrylonitrile sequences are more abundant than expected from random distribution of the monomeric subunits, whereas the relative abundances due to oligomers containing styrene-styrene or acrylonitrile-acrylonitrile sequences are significantly lower than expected for random systems. These results can be explained by the enhanced stability of styrene-acrylonitrile diads.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 120 (1984), S. 163-175 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Pyrolyse-Felddesorptions-Massenspektrometrie ist zur Untersuchung verschiedener Polyamide wie Nylon 6,8,12 und Nylon 66 verwendet worden. Das pyrolytische Verhalten dieser Verbindungen hängt stark vom Lösungsmittel und vom Temperatur-programm ab. Ameisensäure als Lösungsmittel ruft starke thermische Fragmentierung hervor, während mit 1,1,1,3,3,3-Hexafluoro-2-propanol fast ausschließlich Molekülionen oder kationisierte Moleküle gebildet werden. Mit zunehmender Temperatur entstehen größere Cluster der polymeren Untereinheit (Mn + Na)+, aber gleichzeitig nimmt die thermische Fragmentierung auf der Emitteroberfläche zu. Die kationisierten Moleküle sind in allen Spektren dominant. Sie werden von M3 bis M5 oder M15 gebildet, je nach Kettenlange der polymeren Untereinheit. Mit zunehmender Temperatur verschiebt sich der Basispeak des Spektrums zu höheren Massen, und schwache Signale bis m/z 2000 und darüber werden registriert. Thermische Produkte werden hauptsächlich gebildet durch Wassereliminierung (-18 mu), Verlust der Säureamid-Gruppe (-44 mu) nach Umlagerung und von längeren Polyamiden durch Verlust von Methylengruppen (-42 oder 56 mu) durch cis-Eliminierung.Diese thermische Fragmentierung der Polymeren auf der Emitteroberfläche kann durch geeignete Emitterheizung kontrolliert werden und stimmt direkt mit der allgemeinen chemischen Kenntnis von diesen Substanzen in flüssiger und fester Phase überein. Zusammen mit den Vorteilen der integrierten Registrierung, der hohen Massenauflösung und der direkten Isotopenbestimmung ist die Kombination von Pyrolyse und Felddesorptions-Massenspektrometrie hervorragend geeignet zur Charakterisierung von synthetischen Polymeren anhand ihrer Untereinheiten und deren Sequenzen im hohen Massenbereich.
    Notes: Pyrolysis field desorption mass spectrometry has been performed from various polyamides such as nylon 6, 8, 12, and nylon 66. The pyrolytic behaviour of these compounds depends strongly on the solvent and the temperature program employed. Using formic acid as solvent strong thermal fragmentation is observed, while with 1,1,1,3,3,3-hexafluoro-2-propanol almost exclusively molecular ions or cationized molecules of the monomer building block M are produced. With increasing temperature larger clusters of polymeric subunits (Mn + Na)+ are generated, but thermal fragmentation on the emitter surface also increases. The cationized molecules dominate all spectra. They are found from M3 to M5 or M15 depending on the chain length of the polymer subunit. With increasing temperature, the base peak of the spectrum is shifted to the higher mass end and small signals up to m/z 2000 and above are recorded. Thermal products are mainly formed by water elimination (-18 mu), loss of the acid amide group (-44 mu) after rearrangement and from longer polyamides by loss of the methylene groups (- 42 or 56 mu) by cis-elimination.These thermal fragmentations of the polymeric substances on the emitter surface can be controlled by appropriate emitter heating and correlate directly with the common chemical knowledge of these materials in the liquid or solid phase. Together with the options of integrating recording, high mass resolution and direct isotope determination, the combination of pyrolysis and field desorption mass spectrometry offers a unique tool for characterization of building blocks and high mass sequences in synthetic polymers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 14 (1975), S. 403-415 
    ISSN: 0570-0833
    Keywords: Mass spectrometry ; Analytical methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 17 (1978), S. 221-238 
    ISSN: 0570-0833
    Keywords: Mass spectrometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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