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  • Springer  (59)
  • American Society of Hematology  (6)
  • Seismological Society of America (SSA)
  • 1
    ISSN: 1434-4475
    Keywords: Kinetic study ; N-Methylurea ; Nitrosation ; N-Nitroso-N-methylurea
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of nitrosation of Methylurea (MU) in aqueous perchloric solution has been studied using two techniques: a dynamic spectrophotometric and a stopped-flow technique. The rate law obtained, whenpH was varied in the range 0.27–3.22, is $$---d[nitrite]/dt = f[MU][nitrite][H^ + ]/(1 + g/[H^ + ])$$ where [MU] and [nitrite] represent stoichiometric concentrations. At 288.0 K and μ=1.0M,f=(15.6±0.5)M −2s−1 andg=(1.06±0.08) 10−3 M. This rate law becomes independent of the acidity of the solution when this is increased ([ClO4H])〉1.00M). These results together with the activation of the nitrosation rate by the ionic strength and the negative value of the activation entropy shown that only the NO2H2 + or NO+ is the effective carrier for the nitrosation. Comparisons with the nitrosation of dimethylamine were also made leading to the conclusion that there is no simple explanation for the fact that the nitrosation via NO2H2 +/NO+ disappears when the nitrosable compound is of increased basicity.
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  • 2
    ISSN: 1434-4475
    Keywords: Kinetics ; Mechanism ; Mononitrosopiperazine ; N-Nitrosation ; Piperazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Der Mechanismus der Bildung vonN-Nitroso-Verbindungen, die als potentielle carcinogene Substanzen gelten, wurde untersucht. Die Kinetik der Nitrosierung von Piperazin (PIP) in wäßriger Perchlorsäurelösung wurde mittels einer differentiellen spektrophotometrischen Methode verfolgt. Es ergab sich für denpH-Bereich 0,85–4,36 folgendes Zeitgesetz: $$v_0 = \left[ {nitrite} \right]_0 2 \left[ {PIP} \right]_0 /\left( {1 + f/\left[ {H^ + } \right]} \right)^2 \left( {g \left[ {PIP} \right]_0 + h + j\left[ {H^ \div } \right]} \right)$$ wobei [Nitrit]0 und [PIP]0 die anfänglichen stöchiometrischen Konzentrationen bedeuten. Bei 298,2 K und μ=1,0M,f=(1,17±0,11) 10−3 M,g=(3,5±0,7)·10−2 M s,h=2,6·10−6 M 2 s andj=(0,95±0,04)M s. Bei Erhöhung der Acidität ([HClO4]≥1M) tritt ein neuer kinetischer Term auf: $$v_0 ' = p\left[ {Nitrit} \right]_0 \left[ {PIP} \right]_0 $$ Bei 298,2 K und μ=3,0M,p=(1,9±0,2) 10−3 M −1 s−1. Es wird ein genereller Mechanismus für die Nitrosierung jedesN-nitrosierbaren Substrates in wäßriger Perchloratlösung vorgeschlagen, wobei als nitrosierende Agentien ausschließlich N2O3 und H2NO2 +/NO+ auftreten. Es werden die Besonderheiten dieses Mechanismus bezüglich derpK-Werte derN-nitrosierbaren Substrate diskutiert.
    Notes: Abstract The mechanism of formation ofN-nitroso compounds, which are considered as potential chemical carcinogens was studied. The kinetics of nitrosation of piperazine (PIP) in aqueous solution of perchloric acid have been investigated using a differential spectrophotometric technique. Based on our experimental results, the following rate law, in thepH-range 0.85 4.36, is proposed: $$v_0 = \left[ {nitrite} \right]_0 2 \left[ {PIP} \right]_0 /\left( {1 + f/\left[ {H^ + } \right]} \right)^2 \left( {g \left[ {PIP} \right]_0 + h + j\left[ {H^ \div } \right]} \right)$$ where [nitrite]0 and [PIP]0 represent initial stoichiometric concentrations. At 298.2K and μ=1.0M,f=(1.17±0.11) 10−3 M,g=(3.5±0.7) 10−2 M s,h=2.6×10−6 M 2 s andj=(0.95±0.04)M s. When the acidity is increased ([HClO4]≥1M), a new kinetic term comes into play: $$v_0 ' = p\left[ {nitrite} \right]_0 \left[ {PIP} \right]_0 $$ At 298.2 K and μ=3.0M,p=(1.9±0.2) 10−3 M −1 s−1. A general mechanism for the nitrosation of anyN-nitrosable substrate in aqueous perchloric solution in which the only nitrosating agents are N2O3 and H2NO2 +/NO+ is proposed. Also, the various particularities of this mechanism, according to thepK of theN-nitrosable substrate, are discussed.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 127 (1996), S. 537-547 
    ISSN: 1434-4475
    Keywords: Thieno[2,3-c]pyridazine-6-carboxamide ; 5,6,7,8-Tetrahydropyrimido[4′,5′:4,5]-thieno[2,3-c]pyridazines ; 7,8-Dihydropyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines ; Pyrimido[4′,5′:4,5]thieno-[2,3-c]pyridazines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Einfache Synthesen von 3,4-Diphenyl-8-oxo-6-substituierten-5,6,7,8-tetrahydropyrimido[4′,5′:4,5]thieno[2,3-c]pyridazinen (4a-g), 3,4-Diphenyl-8-oxo-6-substituierten-7,8-dihydropyrimido[4′,5′:4,5]thieno[2,3-c]pyridazinen (5a-g), 8-Chlor-3,4-diphenyl-6-substituierten Pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazinen (6a-g) und 3,4,6-Triphenyl-8-substituierten-pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazinen (7a-f) aus 4-Cyano-5,6-diphenylpyridazin-3(2H)-thion (1)via 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (3) werden beschrieben.
    Notes: Summary Convenient syntheses of 3,4-diphenyl-8-oxo-6-substituted-5,6,7,8-tetrahydropyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (4a-g), 3,4-diphenyl-8-oxo-6-substituted-7,8-dihydropyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (5a-g), 8-chloro-3,4-diphenyl-6-substituted-pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (6a-g), and 3,4,6-triphenyl-8-substituted-pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (7a-f) from 4-cyano-5,6-diphenylpyridazine-3(2H)-thione (1)via 5-amino-3,4-diphenyl-thieno[2,3-c]pyridazine-6-carboxamide (3) are reported.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 127 (1996), S. 739-745 
    ISSN: 1434-4475
    Keywords: Pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives ; Thieno[2,3-c]pyridazine-6-carbonitrile ; N,N-Dimethyldichloromethyleniminium chloride ; Enaminonitrile
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wurde ein einfacher Syntheseweg für 8-substituierte Pyrimido[4′,5′:4,5]thieno-[2,3-c]pyridazine entwickelt. Die Reaktion verläuft über den Ringschluß eines heterocyclischen Aminonitrilvorläufers (3) nach Umsetzung mit Dichlormethylen-dimethylammoniumchlorid.
    Notes: Summary A facile synthesis of 8-substituted pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (6a–i) has been accomplished. The sequence involves the ring closure of a heterocyclic aminonitrile precursor (3) after reaction with (dichloromethylene)-dimethylammonium chloride.
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  • 5
    ISSN: 1434-4475
    Keywords: Thieno[2,3-c]pyridazine-6-carboxamide ; Pyridazino[4′,3′:4,5]thieno[3,2-d]1,2,3-triazines ; Pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines ; Pyridazines ; 1,2,3-Triazines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4′,3′:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4′,3′:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).
    Notes: Summary 8,9-Diphenylpyridazino[4′,3′:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4′,3′:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4′,5′:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Naturwissenschaften 78 (1991), S. 224-226 
    ISSN: 1432-1904
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Natural Sciences in General
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  • 7
    ISSN: 1434-4475
    Keywords: Dinitrogen trioxide ; Kinetics of nitrosation ; N-Nitrosation ; Secondary amines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wurde mittels einer differentiellen spektrophotometrischen Methode die Reaktionsgeschwindigkeit derN-Nitrosierung von sekundären Aminen unter Bedingungen untersucht, bei denen N2O3 als nitrosierendes Agens angesehen wird. Der wahre Reaktionsgeschwindigkeitskoeffizientk für denN-Nitrosierungsschritt — sowohl für die oben genannten als auch andere erneut berechnete Systeme mit aliphatischen und aromatischen Substraten mitpK a 〉5 — ergab immer die gleiche Größenordnung von 108 M −1s−1. Dieser Befund zeigt an, daß der Angriff von N2O3 auf die freien Amine diffusionskontrolliert erfolgen muß, wobei diese Annahme auch von den experimentellen Aktivierungsenthalpien von 10–20 kJ/mol gestützt wird.
    Notes: Abstract Using a differential spectrophotometric technique in water at 25°C measurements were made of the reaction rate in the nitrosation of a number of secondary amines in conditions in which the effective nitrosating agent is thought to be dinitrogen trioxide. Analysis of the rate data leads to values ofk, the true rate coefficient for theN-nitrosation step, which, like the values recalculated here for other systems involving aliphatic and aromatic substrates ofpK a 〉5, exhibit the same unvarying order of magnitude, 108 M −1s−1. This figure together with the invariance already mentioned indicates that the attack of the N2O3 upon free amines must be diffusion controlled; this hypothesis is supported by the values found for the enthalpies of activation (10–20 kJ/mol).
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  • 8
    ISSN: 1434-4475
    Keywords: Acetate buffer ; Kinetics of nitrosation ; Morpholine ; N-Nitrosomorpholine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wurde die Kinetik der Nitrosierung von Morpholin in Acetat-Puffer untersucht. Unter den gewählten Reaktionsbedingungen ist das effektive Agens N2O3, dessen Bildung von Acetat-Ionen im Einklang mit dem gezeigten Schema gefördert wird: Zwischen Nitrosylacetat und Amin wurde keine Reaktion beobachtet, vermutlich wegen der niederen Konzentration des ersteren. Der vorgeschlagene Mechanismus erklärt, daß keine Katalyse mittels Puffer unter Bedingungen zu beobachten ist, wo der geschwindigkeitsbestimmende Schritt die Reaktion von N2O3 mit dem Amin ist und daß der katalytische Effekt nur dann beobachtet wird, wenn die Bildung des Nitrosierungsagens geschwindigkeitsbestimmend ist. Gleichgewichts- und kinetische Konstanten, die für den Mechanismus von Bedeutung sind, wurden ermittelt.
    Notes: Abstract The kinetics of the nitrosation of morpholine in acetate buffer have been studied. It was found that in the experimental conditions used the effective nitrosating agent is dinitrogen trioxide, whose formation is promoted by the acetate ion in accordance with the scheme: No reaction between nitrosyl acetate and the a mine was observed, probably owing to the low concentration of the former. The proposed mechanism explains the experimental facts that no catalysis by the buffer is observed in conditions in which the rate controlling step is the reaction of N2O3 with the amine, and that the catalytic effect has only been observed when the formation of the nitrosating agent is also rate controlling. Values have been calculated for several equilibrium and kinetic constants involved in the mechanism proposed.
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  • 9
    ISSN: 1573-9104
    Keywords: Antinutritional factor ; Composition ; Functional property ; Legume ; Protein isolate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Pea (Pisum sativum), faba bean (Vicia faba) and soybean (Glycine max) seeds were characterized, and protein isolates were prepared following an isoelectric point precipitation procedure. Soybean seeds showed the highest protein content (36.7%) and carbohydrate was the major constituent in the pea (59.4%) and the faba bean seeds (52.1%). Protein contents were higher than 80% in all the protein isolates. The amino acid contents in the protein isolates were, in general, higher than those in their own starting seeds. The antinutritional factor contents were reduced after the protein isolate preparation. The highest reductions achieved for tannins were 95% in the faba bean protein isolate, and for phytates (45%) and trypsin inhibitor activity (46%) in the pea protein isolate. Haemagglutinating activity was not detected in any of the protein isolates. Minimum solubility values were observed at a pH range between 4.0 and 6.0, and maximal solubilities were obtained at basic pH values. The faba bean protein isolate showed the highest water and oil absorption capacities, and the best gelling properties. The soybean protein isolate had the best foam expansion capacity. Thus, the protein isolates had an improvement in some of the characteristics compared to their original seeds with lower contents in tannins, phytates and haemagglutinating activity, but had weak functional properties.
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  • 10
    ISSN: 1573-5036
    Keywords: arbuscular mycorrhizal fungi ; isozymes ; nodules ; Pisum sativum ; proteins ; superoxide dismutase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract There are few reports in relation to the role of specific proteins in the mycorrhizal symbiosis. Among the changes in the protein expression as a consequence of the arbuscular mycorrhizal symbiosis, only one case related to changes in superoxide dismutase (SOD; EC 1.15.1.1) activity has been reported in the red clover-Glomus mosseae symbiosis. In this paper, the symbiotic system formed by a leguminous plant,Pisum sativum, and the fungusGlomus mosseae is studied in terms of protein patterns and SOD activity in both mycorrhizal and non-mycorrhizal roots. Our results show that among the differential polypeptides separated by SDS-PAGE, one with a molecular weight of 32.0 kDa, and a protein with an isoelectric point of pI 4.9 appeared strongly expressed in mycorrhizal roots. A partial purification of the related polypeptide could be achieved by DEAE-cellulose chromatography. A higher SOD activity was also detected in mycorrhizal pea roots, although both mycorrhizal and non-mycorrhizal roots showed the same isoenzymatic pattern for SODs: two Mn-SODs (I and II) and two Cu,Zn-SODs (I and II) were detected, Cu,Zn-SOD I being the most abundant isozyme in both types of roots. A similar pattern of SOD isozymes (Mn-SODs I and II, and Cu,Zn-SODs I and II) was also found in nodules of mycorrhizal and non-mycorrhizal pea roots. However, in nodules Mn-SOD II was the main isozyme. The bacterial nature of this isozyme is postulated in this report.
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