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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 13 (1986), S. 217-221 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fragmentations of 2′-, 3′- and 5′-halogenated deoxyribonucleosides were studied using low-resolution mass spectrometry and deuteration experiments. The major reaction pathways provide ions which allow detection of halogen introduction and simple differentiation between the 3′- and 5′-derivatives with respect to the 2′-derivatives. Additionally, it has been shown that the 2′-derivatives from 2,2′-anhydrouridine during the process of evaporation, thus affecting the spectra obtained.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 310-316 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: EPR-Investigations on the Photolysis of Halogenated Organic Compounds I. Pure Halogenated Compounds (CBr4, CHBr3, CCl4 and CHCl3)EPR-spectra of CBr4, CHBr3 and CDBr3, exposed to u.v.-light and γ-rays respectively, are presented. They are discussed and compared with the results of the photolysis of CH2Br2, CH3Br and CCl4, CHCl2, CH2Cl2 and CH3Cl. Under stationary conditions at 77K it was possible to identify paramagnetic species like \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CBr}_4\,^{_{\bar.}} $\end{document}, ·CBr3, ·CH3, ·C2H5, ·CCl3 and trapped electrons.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 317-327 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: EPR-Investigations on the Photolysis of Halogenated Organic Compounds. II. CHBr3 and CBr4 in Glassy and Polycrystalline MatricesPhotolysis of CHBr3, CDBr3 and CBr4 in glassy and polycrystalline matrices (alcohols, diethylether, benzene derivatives and KBr) at T ≥ 77 K yields stationary e.p.r.-spectra in the range of effective g-factor from 2.2 to 1.9. By comparison of the spectra of CHBr3 and CDBr3, exposed to γ-rays and u.v. light respectively, and the spectra of these compounds in matrices it was shown that the photolysis in matrices produces the species \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CBr}_4\,^{_{\bar.}} $\end{document}, ·CBr3 and α-Br-radicals from the halogenated compounds and HĊO, ·CH3, CH3ĊHOH, RĊHOH, and ·C2H5 from the matrix. Photolysis of halogenated compounds in CH3OH and CD3OD yields only HĊO and ·CH3 together with a very small amount of bromine-containing radicals. In all other investigated matrices the concentration of bromine containing species is controlled by physical and chemical properties of the matrix. Time development of the \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CBr}_4\,^{_{\bar.}} $\end{document}-radical and of those generated from the matrix is different and gives insight into the complex photoreaction in solid matrices.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 324 (1982), S. 761-768 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Determination of the Zero Field Parameters Optically Excited 3(π,π*)-States in Selected Aromatic SystemsExperimental zero field parameters of optically excited naphthalene and quinoxaline derivatives are presented. The (D*), (D) and (E) parameters are determined by the position of the transitions by means of simple approximation formula, magnetophotoselection and simulation of spectra. Possibilities of comparison of the zero field parameters of optically excited 3(π,π*)-states with parameters of ground state for simple aromatic hydrocarbones are presented.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 405 (1974), S. 286-298 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: ESR Studies of Radiation Processes in Phosphate GlassesRadiation processes in phosphate glasses are investigated by ESR and optical measurements. ESR shows a hole-centre in the systems K2O/P2O5 and K2O/MGO/P2O5 which depends on manner and concentration of the cations. Its nature is explained in somewhat a different way than given by BEEKENKAMP or by MIURA and HASEGAWA. Another hole-centre which is independent of cations is discussed in agreement with optical investigations. The electrons set free by radiation react with O2 solved in the glass or with cations. The particels Ag0, Ag2+, Ag+2 have been found and Agn+4 may be present too in the system K2O/MgO/Ag2O/P2O5. The system K2O/MgO/Tl2O/P2O5 shows analogous reactions, but full explanation of the lines could not yet be given.
    Notes: Durch ESR-Untersuchungen und Vergleiche mit optischen Messungen werden Aussagen über die durch Bestrahlung in Phosphatgläsern ablaufenden Vorgänge gemacht. In den Systemen K2O/P2O5 und K2O/MgO/P2O5 wird durch ESR-Messungen ein kationenabhängiges Lochzentrum gefunden, dessen Natur in Abweichung von den Modellen nach BEEKENKAMP und nach MIURA u. HASEGAWA erklärt wird. Ein weiteres kationenunabhängiges Lochzentrum wird in Übereinstimmung mit optischen Untersuchungen gedeutet. Die durch Bestrahlung freigesetzten Elektronen lagern sich an im Glas gelösten Sauerstoff (O2) an oder reagieren mit den Kationen. Im System K2O/MgO/Ag2O/P2O5 werden die Teilchen Ag0, Ag2+, Ag+2 gefunden und Agn+4 wahrscheinlich gemacht. Für das System K2O/MgO/Tl2O/P2O5 gelten analoge Verhältnisse. Eine ausführliche Zuordnung konnte aber dabei noch nicht vorgenommen werden.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 472 (1981), S. 220-232 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: EPR Studies of Caminau Kaolin, its Heating Products, and of the Chlorination Products of MetakaolinEPR-spectra of kaolin, metakaolin and of the heating and chlorination products of metakaolin have been measured and partially interpreted. Fe3+ ions are found in kaolin in at least five different coordination conditions. Coordination changes of Fe3+ ions by heating kaolin and tempering metakaolin are reflected sensitively in the EPR spectra. Correlations between EPR spectra of the solid not fluidable chlorination residues and chlorination conditions have been found.
    Notes: Es wurden die EPR-Spektren von Kaolin, Metakaolin sowie von dessen Temper- und Chlorierungsprodukten aufgenommen und z. T. interpretiert. Im Kaolin befinden sich Fe3+-Ionen in mindestens fünf verschiedenen Koordinationszuständen. Die beim Erwärmen des Kaolins, bei dessen Calcinierung sowie beim Tempern des Metakaolins eintretenden Veränderungen werden in den EPR-Spektren empfindlich widersgepiegelt. Zwischen den EPR-Spektren der festen Chlorierungsrückstände und den Chlorierungsbedingungen wurden Zusammenhänge gefunden.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 515 (1984), S. 230-240 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Existence and Structure of Secondary DithizonatesOn example of complexation with copper and palladium proved, that dithizone by double deprotonation forming neutral “secondary” dithiozonates, which have been characterized by elemental analyses, electronic, i.r., ESCA, and EPR spectra and magnetic measurements. Dithizone reacts about ligator atoms N,N′,S. Secondary dithizonates probable are present dimeric.
    Notes: Am Beispiel der Komplexbildung mit Kupfer und Palladium wird nachgewiesen, daß Dithizon unter zweifacher Deprotonierung neutrale, „sekundäre“ Dithizonate bildet, die durch Elementaranalyse, VIS-, IR-, EPR- und Photoelektronen-Spektren sowie magnetische Messungen charakterisiert werden. Dithizon wirkt über die Ligatoratome N,N′,S. Die sekundären Dithizonate liegen wahrscheinlich dimer vor.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 532 (1986), S. 204-214 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: About the Coprecipitation of FeIII and CuII with Bismuth Phosphate and Calcium FluorideThe mechanism of FeIII and CuII coprecipitation with BiPO4 and CaF2 as carriers from ammonium phosphate and ammonium fluoride solutions was investigated. Using the radioactive tracers 59Fe and 64Cu and by means of EPR measurements surface adsorption was shown to be main reason causing coprecipitation. Trace metals distribution was possible to be described by means of Henry and Freundlich isotherms. FeIII and CuII are coprecipitated with BiPO4 as counterions to excess phosphate species at the surface. Differences in the behaviour between these metals are of quantitative nature. CuII is coprecipitated with CaF2 as a counterion to excess F-, whereas FeIII adsorption takes place as FeF63- in competition with matrix fluoride.
    Notes: Es wird das Mitfällungsverhalten von FeIII und CuII aus Ammonium-phosphat- bzw. Ammoniumfluorid-Modellösungen mit den durch Anfällen der Matrices erzeugten Kollektorniederschlägen BiPO4 und CaF2 betrachtet. Radiochemische Untersuchungen mit 59Fe und 64Cu und EPR-Messungen machen deutlich, daß in jedem Fall die Adsorption der Spurenmetalle an der Niederschlagsoberfläche Hauptursache ihrer Mitfällung ist. Die Verteilung zwischen Lösung und Niederschlag läßt sich durch Henry- und Freundlich-Isothermen beschreiben. FeIII und CuII werden mit BiPO4 als Gegenionen zu primär adsorbierten Phosphatspezies mitgefällt. Zwischen beiden Metallen treten Unterschiede quantitativer Art auf. Auch die Mitfällung des CuII mit CaF2 erfolgt als Gegenion, hier zu primär adsorbiertem F-. Das FeIII hingegen wird in Konkurrenz zu den Matrixanionen als FeF63- adsorbiert.
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polarographic Behaviour of Molybdenum(VI) with Special Reference to the Reactions of Molybdenum(V)The reduction of molybdenum(VI) proceeds via molybdenum(V) to molybdenum(III) in sulfuric acid. A dimerization of the formed molybdenum(V) takes place according to a D-mechanism, if hydroxide ligands are involved. The rate of dimerization is large enough to influence the polarographic picture for cH2SO4 〈 2 mol · 1-1 considerably. No experimental reference could be obtained to the existence of molybdenum(IV) during polarography. It was shown, that the preparation of very unstable solutions containing monomeric paramagnetic molybdenum(V) complexes is possible.A summary of the chemical reactions is suggested.
    Notes: Die Reduktion von Molybdän(VI) führt in Schwefelsäure über Molybdän(V) zu Molybdän(III). Enthält das sich zunächst bildende monomere Molybdän(V) Hydroxidliganden, so erfolgt eine Dimerisierung nach dem D-Mechanismus. Diese Dimerisierung ist für cH2SO4 〈 2 mol · 1-1 so schnell, daß das polarographische Bild entscheidend durch diesen Prozeß geprägt wird. Während der Reduktion gibt es keine Hinweise für das Auftreten von Molybdän(IV). Unbeständige Lösungen monomerer paramagnetischer Molybdän(V)-Komplexe konnten erhalten werden.Ein zusammenfassendes Reaktionsschema wird vorgeschlagen.
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  • 10
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Effect of Different Oxidation States of Nickel and Chromium in Heterogenous Halogen ExchangeNi-doted AlF3 catalysts and chromium oxide fluoride catalysts being used for production of C—Cl—F compounds from chlorocarbons by reaction with HF have been investigated by EPR. There are different oxidation states of Ni resp. Cr at the catalysts which show exchange behaviour. Extending the consumptions of mechanisms for heterogeneous Cl—F exchange the oscilation of oxidation state and therefore the exchange in donor-acceptor functions at the catalysts is said to be the cause for the effectiveness of the catalysts. It is presumed that this exchange of oxidation states is of general importance for catalytic processes with heterolytic bond cleavage.
    Notes: Mit der Hilfe von EPR-Messungen wird an Ni-beladenen AlF3-Katalysatoren die Gegenwart von Ni3+ neben chemisch nachgewiesenem Ni2+ und an Chromoxid-Gel-Katalysatoren die Austauschwechselwirkung zwischen CrIII und höheren Oxydationsstufen des Chroms aufgezeigt. Beide Katalysatortypen sin zur Herstellung von C—Cl—F-Verbindungen aus Kohlenstoffchloriden mittels HF geeignet. In Erweiterung von Vorstellungen zum Mechanismus des heterogen-katalytischen Cl—F-Austauschs wird die Oszillation der Oxydationsstufen and damit der Wechsel in Donor-Akzeptor-Funktionen am Katalysator für die Effektivität der Katalysatoren verantwortlich gemacht. Es wird auf die allgemeine Bedeutung dieses Mechanismus hingewiesen.
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