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  • Organic Chemistry  (5)
  • agricultural soil management  (1)
  • field experiment  (1)
  • 1
    ISSN: 1572-9729
    Keywords: agricultural soil management ; chemical characterization ; organomineral bonds ; particle-size fractions ; pyrolysis-mass spectrometry ; soil organic matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The formation of soil organic matter from grass residues was studied in a 34-year-old pot experiment with grass cultivation on loamy marl using pyrolysis-field ionization mass spectrometry (Py-FIMS). For whole soils, the Py-FI mass spectra indicated clear changes in the molecular-chemical composition during SOM formation from grass residues. In particular, the enrichment of heterocyclic N-containing compounds with time was remarkable. For organomineral size fractions, even larger differences in the composition of SOM were found. The changes between the 13th and 34th experimental year are partly explained by a net transfer of phenols, lignin monomers and lignin dimers from medium silt to fine silt. Moreover, it is demonstrated that temperature-resolved Py-FIMS enables the determination of the thermal energy required for the evolution of individual compound classes which is a measure of the strength of humic- and organomineral bonds. At lower temperatures (〈 400 °C), the enrichment of thermally less stable and/or loosely bound organic matter with cultivation time in clay and fine silt is due to carbohydrates, N-containing compounds, phenols and lignin monomers. Shifts of evolution maxima toward a higher pyrolysis temperature (〉 400 °C) in clay, fine silt and medium silt are explained by a higher thermal stability of humic and/or organomineral bonds of lignin dimers, alkylaromatics and lipids, that developed during the last two decades of the experiment.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Plant and soil 160 (1994), S. 225-235 
    ISSN: 1573-5036
    Keywords: fertilization ; field experiment ; organic carbon ; particle-size fractions ; pyrolysis-mass spectrometry ; seasonal variations ; soil organic matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Seasonal variations of soil organic matter (SOM) were studied in the unfertilized plot (U) and in the NPK+farmyard manure plot (NPK+FYM) of the 88-year-old ‘Static Experiment’ at Bad Lauchstädt (Germany). Decreases in the C concentrations by 0.24% (U) and 0.43% (NPK+FYM) between June and August were observed which were significant at the p 〈 0.01 level. The largest differences in N concentrations were 0.035% (U: August vs. September) and 0.029% (NPK+FYM: April vs. May). The C/N ratios were lowest in July and August (∼12). The seasonal variations of SOM contents were reflected in significant differences in the C concentrations of organo-mineral particle-size fractions. The proportions of soil C, associated with clay increased from 56% and 38% in April to 69% and 48% in October in the untreated and NPK+FYM-treated plot, respectively. Pyrolysis-field ionization mass spectra of whole soil samples taken in June and August showed larger differences in the molecular composition of SOM in the untreated plot than in the NPK+FYM plot. On the basis of thermograms for six important compound classes of SOM, seasonal variations in (a) their amounts and (b) their incorporation in thermally different stable humic and/or organo-mineral bonds were visualized. Within four weeks of a net mineralization of SOM, portions of phenols, lignin monomers, lignin dimers, alkylaromatics, lipids, N-containing compounds and carbohydrates reached a higher thermal stability, which can be explained by advanced crosslinking. These results represent the first application of this novel methodology to the subtle and difficult problem of seasonal SOM variations.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Heart Glycosides of the Arrow Poison of Lophopetalum toxicum LOHERFrom the cytotoxic and positive inotropic acting bark extract of the Philippinan Lophopetalum toxicum eight heart glycosides have been isolated and their structures have been elucidated mainly by field-desorption-MS- and 1- and 13C-NMR spectroscopy. Besides the known k-Strophanthidin (1), Antiarigenin (6) and β-Antiarin (Antiarigenin-3-β-O-α-L-rhamnoside, 10) the following mono- and diglycosides could be identified: strophanthidin-3-β-O-α-6-desoxy-D-allopyranoside (strophalloside, 2), strophanthidin-3-β-O-β-6-desoxy-D-glucopyranoside (= Strophanthidin chinovoside, 3), strophanthidin-3-β-O[-4Oβ-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (4), strophanthidin-3-β-O-[3-O-β-D-glucopyranosyl-β-6-desoxy-D-talopyranoside] (5), antiarigenin-3-β-O-[3-O-β-D-gulopyranosyl-β-6-desoxy-D-talopyranoside] (7), antiarigenin-3-β-O-[4O-β-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (8), and antiarigenin-3-β-O-β-6-desoxy-D-allopyranoside (antiallosid) (9). The structure of strophanthidinchinovoside (3) could be confirmed by synthesis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Analogy of Sugar Cleavages from Oligoglycosidic Natural Products by Acidic Solvolysis in Solution Chemistry and Field Desorption Mass SpectrometryThe experimental conditions for inter-laboratory reproducibility of field desorption mass spectrometry (FD-MS) for molecular weight determination and structural analysis of organic natural products were evaluated: using trillenoside B (1) as an example, the cleavages of the terminal sugar units were qualitatively and quantitatively investigated by two research groups using different instruments. The known optimal instrumental parameters then allowed parallel investigations of other oligoglycosides such as zizyphussaponin-1 (2), methyl protodioscin (3), and protodioscin (4). In accordance with the proton-induced fragmentation in FD-MS it was possible to produce by stepwise, partial acid hydrolysis three derivatives of ebelin lactone from the saponin 2. Also compound 3 treated in the same manner gave in both cases pseudodiosgenin-3,26-bis(glycoside) (5). These studies gave the first chemical evidence of the proton-induced cleavage of the glycosidic bond and the production of sequence-specific fragments in field desorption and thus confirmed its analogy.
    Notes: Um die Bedingungen für die Reproduzierbarkeit der Molekulargewichtsbestimmung und Strukturanalyse von Naturstoffen mittels Felddesorptions-Massenspektrometrie (FD-MS) kennenzulernen, wurden am Beispiel von Trillenosid B (1) durch zwei Arbeitsgruppen mit verschiedenen Instrumenten die Abspaltungen der terminalen Zucker qualitativ und quantitativ untersucht. Unter den abgestimmten apparativen Bedingungen wurden dann die Oligoglykoside Zizyphussaponin-1 (2), Methylprotodioscin (3) und Protodioscin (4) parallel studiert. übereinstimmend mit den erhaltenen Ergebnissen der Protonen-induzierten Fragmentierung bei FD-MS konnten durch abgestufte, partielle Säurehydrolyse aus 2 drei verschiedene Glykoside des Ebelinlactons erhalten werden. Aus 3 lieβ sich entsprechend nach beiden Verfahren Pseudodiosgenin-3,26-bis(glykosid) (5) erhalten. Damit wurden erstmals die Protonen-induzierte Spaltung der glykosidischen Bindung und die Erzeugung sequenzspezifischer Fragmente beim Prozeß der Felddesorption chemisch nachvollzogen und deren Analogie bestätigt.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Knowledge of the Corrin Chromophore, IV. - Partial, Reversible Ring Cleavage of Dicyano-cobyrinic Heptamethyl Ester with Intermediate Reversible Removal of Cobalt
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Biologically Active Glycosides from Asteroidea, I1).  -  Structures of a New Cerebroside Mixture and of Two Nucleosides from the Starfish Acanthaster planciFrom the starfish Acanthaster planci the new cerebroside mixture 1 (11.7 mg per individual of average weight 150 g) and the two nucleosides 2 (2.4 mg per individual) and 3 (1.1 mg per individual) have been isolated. Acid catalyzed methanolysis of 1 afforded the methyl esters of four α-hydroxy fatty acids [tetracosanoate (major component), tricosanoate, docosanoate, and nonadecanoate], two 2-amino-1,3,4-alkanetriols [heptadecanetriol (major component) and octadecanetriol], and methyl glucoside. The nucleosides 2 and 3 have been identified as thymine deoxyribonucleoside and uracil deoxyribonucleoside, respectively. Apart from conventional analytical methods, field desorption mass spectrometry (FD-MS) was successfully used for the first time for the determination and confirmation of the structures of naturally occurring glycolipids and nucleosides.
    Notes: Aus dem Seestern Acanthaster planci wurden das neue Cerebrosidgemisch 1 (11.7 mg pro Individuum bei einem mittleren Körpergewicht von 150 g) sowie die beiden Nucleoside 2 (2.4 mg pro Individuum) und 3 (1.1 mg pro Individuum) isoliert. Die säurekatalysierte Methanolyse von 1 ergab die Methylester von vier α-Hydroxyfettsäuren [Tetracosanoat (Hauptbestandteil), Tricosanoat, Docosanoat und Nonadecanoat] zwei 2-Amino-1,3,4-alkantriole [Heptadecantriol (Hauptbestandteil) und Octadecantriol] sowie Methylglucosid. Die Nucleoside 2 und 3 wurden als Thymindesoxyribonucleosid bzw. Uracildesoxyribonucleosid identifiziert. Neben den konventionellen analytischen Methoden wurde erstmals die Felddesorption-Massenspektrometrie (FD-MS) für die Bestimmung und Absicherung der Struktur natürlich vorkommender Glykolipide und Nucleoside erfolgreich eingesetzt.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von Desoxyoligonucleotid-Fragmenten zur Anwendung in der Genverknüpfung unter Einsatz verbesserter präparativer und analytischer MethodenZur Untersuchung der Expression rekombinanter DNS haben wir Oligonucleotide als Genverknüpfungsfragmente dargestellt, die spezifische Spaltstellen sowohl in die DNA wie in das zugehörige Protein einführen. Ihr Aufbau ist so, daß die Spaltung eines Fusionsproteins entweder durch Bromcyan oder durch Kollagenase erfolgen kann. Die Synthese wurde nach dem Triesterschema durchgeführt, wobei schnellere und einfachere Wege zu funktionalisierten Dinucleotid-Baueinheiten entwickelt wurden. Die Felddesorptions-Massenspektrometrie diente als Routine-methode für den Strukturbeweis und die Reinheitskontrolle dieser Baueinheiten.
    Notes: For studies on the expression of recombinant DNA, linker fragments have been prepared which serve to introduce specific points of cleavage on the DNA as well as the protein level. Such linkers were designed for cyanogen bromide as well as for collagenase cleavage of fused proteins. The preparation was done according to the triester synthesis scheme using improved and simpler routes to functionalized dinucleotide building blocks. Field desorption mass spectrometry was used as a routine tool for the identification and control of the purity of these units.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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