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  • 1
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1551-2916
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: 27Al–MAS (magic angle spinning)–NMR and Fe3+ EPR measurements have been performed to follow the local process of corundum formation starting from xerogel on the Al3+ and Fe3+ sites yielding complementary information. Different heat treatments have been applied to the samples: an isochronous procedure and thermoanalytical measurements stopped by quenching. Despite the different mechanisms of the phase transitions deduced, both seeding and Fe3+ doping under the conditions of isochronous procedure favor the formation of α-Al2O3 at remarkably low temperatures. The first observed temperature of corundum formation following the isochronous procedure with iron-doped samples is as low as 750°C. The transition alumina, which could be clearly evidenced, is the γ-Al2O3 phase (four- and six-fold Al coordination). In undoped or unseeded samples, intermediate Fe species could be detected by ESR and evidence for θ-Al2O3 was obtained from 27Al–NMR spectroscopy.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1420-908X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract CuZn superoxide dismutase (CuZnSOD) contributes to the regulation of the steady-state concentration of reactive oxygen species in cells and minimizes pathological consequences induced by these reactive oxygen species. During the exaggerated formation of reactive oxygen species, often resulting from an activation of phagocytotic cells, CuZnSOD is administered with a therapeutic purpose. But inhibition of the endogeneous or administered CuZnSOD by products generated during the process of formation of reactive oxygen species (H2O2, HOCl, · OH, products of lipid peroxidation) might intensify cell damage. In this study, we compared the influence of malondiadehyde (MDA, high reactive molecule formed in lipid peroxidation) and H2O2 (known to inhibit the CuZnSOD) on bovine CuZnSOD. MDA reacted with CuZnSOD. The reaction was found to be both time- and concentration-dependent, which was demonstrated by the formation of fluorophors. EPR spectroscopy revealed that this reaction had no influence on the activity of CuZnSOD since the catalytic centre of the CuZnSOD was not effected by MDA. In contrast, H2O2 modified the catalytic centre which caused an activity decrease.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1438-2385
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Description / Table of Contents: Zusammenfassung ESR spektroskopische Untersuchungen zum Mechanismus der Maillard-Reaktion am Modelld-Glucose/Glycin belegen den radikalischen Verlauf einiger Reaktionsschritte, möglicherweise in Konkurrenz zu ionischen Mechanismen. Die Bildung von Radikalen ist abhängig von der Konzentration der Reaktanten und durchläuft in thermisch-induzierten Bräunungsreaktionen ein Maximum. Der Zusatz vonl-Cystein bewirkt eine 60%ige Reduzierung der Konzentration an Radikalen und beweist somit indirekt deren Beteiligung bei der Bildung von Bräunungsprodukten. Die Analyse der Hyperfein-struktur der ESR-Spektren läßt Pyrazinkationradikale vermuten.
    Notes: Summary ESR spectroscopic investigations on the mechanism of Maillard-reactions using the modeld-glucose/glycin show radical formation in some of the reaction steps. These are possibly due to competitive reactions against ionic mechanism. The formation of radicals depends on the concentration of reactants and reaches a maximum in thermically induced browning reactions. The addition ofl-cysteine leads to a decrease in the radical concentration to about 60%. It can be indirectly proven that the radicals are involved in the formation of browning products. The hyperfine structures of ESR spectra are supposed to be similar to pyrazine cation radicals.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 113 (1982), S. 973-983 
    ISSN: 1434-4475
    Keywords: Binuclear compounds ; EPR-Spectra simulation ; Hydrodynamic radii ; 15N-Labeled compounds ; Reorientation correlation time
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The EPR spectra of Cu(II)-complexes of substituted 4-R-phenyl-aminomethylene-Δ2-pyrazolinones-(5) [R = N(CH3)2,p-OCH3, H,p-Cl,p-NO2] were obtained using polycrystalline samples and solutions. The spin-Hamiltonian parameters $$\tilde g, \tilde A, \tilde D$$ and theDebye radii have been determined. In toluene mononuclear and binuclear species can be detected. The Cu-Cu-distance has been estimated to be 0.43 nm.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of materials science 25 (1990), S. 223-232 
    ISSN: 1573-4803
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract By means of EPR, susceptibility, EMP, light-microscopic, thermal and chemical methods the influence of production conditions and subsequent treatments on glassy-phase-containing corundum materials were studied. Melting of the system (Al2O3, SiO2, Na2O, Fe3O4) under reductive conditions leads to a reduction of Fe3+ species contained to Fe2+ and even to Fe0 clusters with ferromagnetic behaviour. Both species markedly influence the mechanical properties of the material by increase of their volumes in consequence of oxidation in subsequent thermal processes. The following model with regard to the localization of the iron species in the system ensues: Fe(III) in corundum, Fe2O3, Fe3O4 and (scarcely) in the glassy phase; Fe(II) in the glassy phase, FeAl2O4 (hercynite) as a solid solution in corundum, and Fe3O4; (Fe0) clusters in corundum. It is therefore not surprising that grinding of the compact material considerably alters the magnetic properties of the samples.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 1567-1576 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The hydrophilicity of poly(vinyl alcohol) (PVA) was lowered by acetalization with propionic aldehyde. After UV irradiation of pendent styrylpyridinium groups, these prepolymers form networks of different hydrophobicity depending on the degree of acetaization. PVA films containing different amounts of propionic acetals were doped with 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Then, the ESR spectra of the spin probe entrapped in the polymeric network were monitored while allowing different solvents to diffuse into the polymer. The rate of spin probe mobilization depends on the hydrophilicity/hydrophobicity of both the polymer network and the solvent. However, the modified polymers, even the more hydrophobic ones, are hydrophilic in comparison to “really” hydrophobic polymers. This is probably caused by the character of the parent polymer (PVA), unreacted hydroxy groups. S++uiations of the ESR spectra have shown that in polymers with a higher degree of acetalization domains of different hydrophobicity are built in which the spin probes have a different mobility. © 1995 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of tert-butyl hydroperoxide by photochemically induced reactions in DMSOAbbreviations used: DMSO, dimethyl sulfoxide; DMSO-d6, completely deuterium labelled dimethyl sulfoxide; cw-ESR, continuous-wave Electron Spin Resonance; u. v., ultra violet; DMPO, 5, 5-dimethyl-I-pyrroline N-oxide; TMPO, 3, 3, 5, 5-tetramethyl-l-pyrroline N-oxide. and water was investigated by cw-e.s.r. spectroscopy. The products tert-butylperoxyl, methyl and sulfur-centered free radicals were identified. The tert-butoxyl free radical is involved in the primary process as shown by time-resolved e.s.r. technique. On the basis of directly identified radical species, a mechanism for the photochemically induced reactions of tert-butyl hydroperoxide in DMSO is proposed. At concentrations below 0.8 mol · l-1 the radical formation from tert-butyl hydroperoxide proceeds by cleavage of the O—O bond rather than by hydrogen abstraction.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 319 (1977), S. 755-761 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Relaxation Processes in Optically Excited EDA Complexes of TCNEThe quenching of fluorescence of aromatic π-donors by TCNE served as an qualitative criterion for the participation of excited states of EDA complexes in deactivation processes in solution. Due to the energetic situation of the states taking part in deactivation the quenching process in the chosen TCNE-donor complexes is controlled by diffusion. In unpolar solvents and in the presence of oxygen phosphorescence of donors and ionic dissociation of EDA complexes was not be observed. While at 25°C the deactivation of the EDA excited states occurs mainly radiationless, the appropriate CT fluorescence emissions at - 196°C are evident.
    Notes: Als qualitatives Kriterium für die Beteiligung angeregter Zustände von EDA-Komplexen am Desaktivierungsprozeß diente in Lösung die Löschung der Fluoreszenz aromatischer π-Donatoren durch Tetracyanoäthen (TCNE) als Elektronenakzeptor. Auf Grund der energetischen Lage der an der Desaktivierung beteiligten Zustände verläuft dieser Löschprozeß in den ausgewählten TCNE-Donator-Komplexen diffusionskontrolliert. Dabei ist in unpolaren Lösungsmitteln bei Sauerstoffanwesenheit keine Phosphoreszenz der Donatoren bzw. ionische Dissoziation der EDA-Komplexe nachweisbar. Während bei 25°C die Desaktivierung des EDA-Anregungszustandes ausschließlich strahlungslos erfolgt, werden bei-196°C an einigen TCNE-Komplexen die entsprechenden CT-Fluoreszenzen beobachtet.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 319 (1977), S. 827-834 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Discussion of the EPR-Spectra of TCNQ and TCNE Radical Anions on the Basis of Solvent ParametersThe formation and stabilization of TCNQ and TCNE radical anions as well from neutral molecules as from EDA complexes in solution was investigated by EPR spectroscopy. The remarcable dependence of generated radical anion concentration, line width and resolution of EPR signals from the nature of used solvents was explaint in terms of selected solvent parameters. It was shown, that the donicity is a proper parameter for characterizing the generation of radical anions, whereas the parameters acceptor number and the quantity δ, which is proportional to the energy of solvent cage formation, can be used as a measure for stabilization of the generated radical anions in solution.
    Notes: Die Bildung und Stabilisierung von Radikalanionen des TCNQ und TCNE sowohl aus den neutralen Akzeptoren als auch aus EDA-Komplexen in Lösung wurde EPR-spektroskopisch untersucht. Die z. T. erhebliche Abhängigkeit der Konzentration an gebildeten Radikalanionen, der Linienbreite der EPR-Linien und der Auflösung der Hyperfeinstruktur von der Art des verwendeten Lösungsmittels konnte mittels ausgewählter Solvensparameter interpretiert werden. Als geeignete Parameter für die Radikalanionenbildung erwies sich hierbei die Donizität, während die Parameter Akzeptorzahl und die Größe δ, die der Energie zur Ausbildung eines Lösungsmittelkäfigs proportional ist, als Maßzahl für die Stabilisierung der gebildeten Radikalanionen in Lösung herangezogen werden konnten.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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