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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden bei teinochemisch aktiven Systemen allgemeine und quantitative Beziehungen begründet zwischen den für die chemische Erzeugung von Längenänderungen erforderlichen Stoffmengen, dem Elastizitätsmodul und der Verschiebung chemischer Gleichgewichte, welche beim mechanischen Dehnen solcher Systeme auftritt. Die allgemeinen Beziehungen werden auf den Fall der homogenen, Polyvinylalkohol und Polyacrylsäure enthaltenden Gele (homogener pH-Muskel) spezialisiert und angewendet.
    Additional Material: 4 Ill.
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zwecks Klarstellung der Vorgänge, welch sich bei der Erzeugung von mechanischer aus chemischer Energie durch Kontraktion von aus Polyvinylalkohol und Polyacrylsäure bestehenden homogenen Lamellen abspielen, werden, ausser der Herstellung, eine Reihe von Eigenschaften dieser Folien beschrieben.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 45 (1962), S. 2325-2342 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden die Kriterien präzisiert, mit deren Hilfe die quantitative Umwandlung von freier chemischer Energie in mechanische Energie durch kontraktile Systeme theoretisch und insbesondere auch experimentell sichergestellt werden kann. Es wird zu diesem Zwecke ein (teinochemisches) System betrachtet, welches aus einer kontraktilen Lamelle und einer Einbettungsflüssigkeit besteht. Der Möglichkeit, durch Zusatz chemischer Reagentien zur Einbettungsflüssigkeit eine reversible Kontraktion und Dilatation der Lamelle zu bewirken, steht immer die komplementäre Erscheinung zur Seite, dass bei mechanischer Dehnung der Lamelle eine Veränderung chemischer Gleichgewichte und damit verbunden eine Erhöhung der Aktivität der die Kontraktion bewirkenden bzw. eine Erniedrigung der Aktivität der die Dilatation bewirkenden Reagentien in der Einbettungsflüssigkeit eintritt. Eine quantitative Koppelung der beiden Phänomene (Längenänderung bei Zusatz chemischer Reagentien und Änderung der Aktivität in der Einbettungsflüssigkeit bei mechanischer Dehnung der Lamellen) ist Voraussetzung und Kriterium für eine quantitative Umwandlung von freier chemischer in mechanische Energie. Die diese Zusammenhänge beschreibenden quantitativen Beziehungen werden formuliert und begründet, und zwar auch in dem praktisch interessierenden Fall, dass im System nebeneinander verschiedene teinochemisch aktive Substanzen vorkommen. Für jede teinochemisch aktive Substanz besteht eine (partiell) für die hervorgehobene Substanz gültige Beziehung, eine Beziehung, welche ihrerseits von den zu präzisierenden Versuchsbedingungen abhängt. Von Interesse ist eine Beziehung (Total-System-Gleichung), durch welche verbunden werden: 1. die Menge an hervorgehobener teinochemisch aktiver Substanz, welche dem aus Gelfaden und Einbettungsflüssigkeit gebildeten Gesamtsystem zuzusetzen ist, um an dem nicht oder mit einer konstanten Kraft k1 belasteten Gelfaden eine Längenänderung von der Grösse 1 zu erzielen; 2. die Änderung der Kraft, welche notwendig ist, um an dem in der Einbettungsflüssigkeit befindlichen Faden die Längenänderung 1 herbeizuführen; und 3. die Änderung des Logarithmus der Aktivität der hervorgehobenen Substanz, welche (durch Messung in der Einbettungsflüssigkeit) festzustellen ist, wenn der Faden unter Konstanthaltung aller im Gesamtsystem vorhandenen Molzahlen mechanisch um eine Längeneinheit gedehnt wird.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 60 (1977), S. 1247-1255 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Structure of Cyclosporin CThe structure of cyclosporin C (2), a minor antifungal metabolite from Trichoderma polysporum (Link ex Pers.) RIFAI has been elucidated. Hydrolytic cleavage and spectroscopic evidence show that cyclosporin C is a neutral oligopeptide of 11 amino acids linked together in a 33-membered ring. Cyclosporin C (2) differs from the main metabolite cyclosporin A (1) [2] [4] only by containing L-threonine in the place of L-α-aminobutyric acid as has been shown by the conversion of 2 into 1. 13C-NMR. spectra and study of molecular models suggest that cyclosporin C (2) has the same molecular conformation as 1, which is best described as a twisted β-pleated sheet held together in a conformationally stable form by intramolecular hydrogen bonding.
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  • 5
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Cyclopeptides from Trichoderma polysporum (LINK EX PERS.) RIFAI: Cyclosporins B, D and ECyclosporins represent a new group of biologically active metabolites produced by Trichoderma polysporum (LINK EX PERS.) RIFAI and other fungi imperfecti. The structures of the main components, cyclosporins A (1) and C(3) have been determined as neutral cyclic oligopeptides composed of 11 amino acids, among them a new C9-amino acid [2-4]. In addition, three minor metabolites, cyclosporins B, D and E, have now been isolated and characterized. Chemical investigation, spectroscopic evidence and X-ray analysis led to the structural formulae of cyclosporins B (2) and D (4). Both compounds have the same sequence of amino acids as cyclosporin A (1), with the exception of L-α-aminobutyric acid, replaced in cyclosporin B (2) by L-alanine and in cyclosporin D (4) by L-valine, respectively. Cyclosporins undergo a characteristic intramolecular N,O-acyl migration to furnish the corresponding basic isocompounds. The antifungal activities of cyclosporins are reported.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An arrangement for light induced vectorial charge separation is discussed in which the electron of the excited dye is transferred to an acceptor and the dye is recovered by electron tunneling through a high and narrow potential barrier. The possible relevance of the model in connection with photosynthesis is considered. Monolayers of Ru(II)-bipyridine complexes with long chain hydrocarbon substituents were investigated which may be useful as component in such arrangements.The surface pressure area isotherms of the monolayers were measured for various ionic compositions of the subphase, and the results demonstrate a strong effect of these ions on the structure of the layers. The layers were deposited on different substrates. The luminescence and its change by contacting the sample with water and by subsequent drying were found to be strongly dependent on the architecture of the layer assembly. Attempts of a photochemical cleavage of water with these assemblies failed.The pH-dependence of the absorption and the luminescence of a Ru(II) bipyridine-dicarboxylic acid complex in solution is interpreted by assuming that the electron in the excited state is localized in one pyridine part of the substituted ligand, the conjugation with the second half of the bipyridine carboxylic acid being negligible. Monolayer assemblies for measuring the energy transfer from the ruthenium complex to an adequate energy acceptor and from an adequate energy donor to the ruthenium complex were investigated. The results demonstrate that the deactivation of the excited ruthenium complex occurs mainly by passing the luminescent state.Assemblies were investigated for measuring the electron transfer from the excited ruthenium complex to an appropriate electron acceptor positioned in the carboxylate portion at the same interface as the electron donor. With bipyridinium ions as acceptor the ruthenium complex luminescence is quenched at average distances between acceptor molecules of about 10 Å, while this distance is 30, 60 und 75 Å for different cyanine dyes used instead of the ruthenium complex. A correlation between this distance and the ionization energy in the excited state of the donor is observed.
    Additional Material: 11 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclosporin A, a Peptide Metabolite from Trichoderma polysporum (LINK ex PERS.) Rifai, with a remarkable immunosuppressive activityTwo antifungal metabolites, cyclosporins A and C, were isolated from a strain of Trichoderma polysporum (LINK ex PERS.) Rifai. Cyclosporin A, the main component, has the molecular formula C62H111N11O12 as deduced by NMR. and mass spectra. Hydrolytic cleavage of cyclosporin A furnished 11 amino acids as fragments, among them an artefact of a new C9-amino acid. The amino acid sequence was determined by Edman degradation of iso-cyclosporin A, a basic rearrangement product formed from cyclosporin A by N, O-acyl migration. In an independent investigation an X-ray analysis of the iodo derivative 10 was performed (see the following paper). On the basis of the chemical, spectroscopic and crystallographic evidence the complete structure of cyclosporin A was elucidated as the neutral cyclic oligopeptide 1. Cyclosporin A and C show remarkable immunosuppressive and antiphlogistic activities in several pharmacological models.
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclopeptide antibiotics from Aspergillus species. Structure of echinocandins C and DThe echinocandins B, C and D are antifungal antibiotics produced by a strain of Aspergillus rugulosus. All three metabolites are closely related representing cyclic oligopeptides composed of six amino acids and a linolic acid residue in an amide linkage. The complete structure of echinocandin B (1) has recently been established by X-ray analysis. Structural assignments to the new minor metabolites C and D have now been made by hydrolytic and oxidative cleavage reactions, formation of N-acyl-α-aminoethers as well as by chemical correlations and extensive NMR. examinations. Echinocandin C (2), C52H81N7O15, contains 3-hydroxyhomotyrosine in the place of 3, 4-dihydroxyhomotyrosine present in 1. Echinocandin D (3), C52H81N7O13, differs in two amino acids: 3, 4-dihyroxyhomotyrosine and 4, 5-dihydroxyornithine, unusual units of 1 being replaced by 3-hydroxyhomotyrosine and ornithine.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 43 (1960), S. 989-1004 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird eine fünfstufige Präzisions-Destillationsanlage beschrieben, in welcher durch Destillation von Wasser, ausgehend von natürlichem Wasser, die Sauerstoff-isotopen 17O und 18O, gegenwärtig mit Konzentrationen bis zu 0,9% 17O und 93% 18O, in grösseren Mengen gewonnen werden. Der Konzentrationsverlauf der Sauerstoffisotopen ist in Abhängigkeit von der effektiven Trennstufenzahl der Destillationsanlage dargestellt. Ein Vergleich der gemessenen Konzentrationsverläufe mit den für das ternare Gemisch H216O, H217O und H218O berechneten Kurven zeigt eine gute Übereinstimmung der gemessenen und berechneten Werte. Ebenfalls ist die mit der Konzentrierung der Sanerstoffisotopen parallel laufende Konzentrierung des Deuteriums beschrieben.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 45 (1962), S. 868-881 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to elucidate the structure of its sugar moiety, digitoxin (I) has been permethylated. Since it was not possible to isolate a homogeneous O-methyl derivative of (I) the mixture of permethylation products was degraded by hydrolysis. As parts of the sugar moiety, 3,4-di-O-methyl-D-digitoxose (III) and D-cymarose (IV) could be isolated in a 1:2 ratio.
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