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  • Wiley-Blackwell  (114)
  • 1980-1984  (18)
  • 1950-1954  (96)
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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Während bei Gesamtheiten von Fadenmolekeln für die Beschreibung der praktischen Eigenschaften, sowie für die Diskussion verschiedener Mittelwerte der einzelne Molekelfaden durch ein aus Nm geradlinigen, statistisch aneinandergefügten Fadenelementen der Länge Am bestehendes Modell beschrieben werden kann (Knickmodell), sind in vorangehenden Arbeiten bei der Durchführung von Modellversuchen über das hydrodynamische Verhalten von Fadenmolekeln an Stelle von Knickmodellen etwas anders geartete Modelle, die als Segmentmodelle bezeichnet werden können, verwendet worden. Solche, aus Draht bestehende Segmentmodelle werden dadurch erhalten, dass man einen Draht der Länge L = Nσ Bσ in Nσ Abschnitte je der Länge Bσ einteilt und jedem dieser Abschnitte in statistischer Weise durch Krümmen des Drahtes die Gestalt eines Kreissegments erteilt, genauer gesagt so, dass die Richtung der Tangente im Anfangspunkte des Segmentes zur Richtung der Tangente im Endpunkt eines herausgegriffenen Segmentes statistisch orientiert ist. Die Herstellungsweise dieser aus Kreissegmenten bestehenden Modelle wird beschrieben und näher begründet. Bei der näheren Diskussion und beim Vergleich der Parameter, welche diese Segmentmodelle einerseits, die Knickmodelle andererseits charakterisieren, ergeben sich gewisse Korrekturen an Ansätzen, dic in vorangehenden Arbeiten benützt worden waren. Diese Korrekturen wirken sich auf die Werte der von uns bisher verwendeten Beziehungen über Diffusion, Sedimentation, Viskosität und Strömungsdoppelbrechung aus. Die Ausdrücke, die sich nach Anbringen der angedeuteten Korrekturen in den Zahlenfaktoren dieser Beziehungen ergeben, werden zusammengestellt. Es zeigt sich, dass auf Grund der korrigierten Beziehungen über Diffusion, Sedimentation und Viskosität eine bessere übereinstimmung von Theorie und Experiment festzustellen ist als auf Grund der bisher verwendeten Ausdrücke. Insbesondere zeigt sich, dass gewisse bisher aufgetretene Diskrepanzen zwischen den aus Diffusion und Sedimentation einerseits, aus Viskosität anderseits ermittelten Werten der Länge Am des statistischen Vorzugselementes nach Anbringen dieser Korrekturen verschwinden.
    Additional Material: 9 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 36 (1953), S. 1209-1231 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird ein Apparat beschrieben, mit welchem die Orientierung und der Betrag der Strömungsdoppelbrechung durch je eine Halbschattenvorrichtung bestimmt werden können. Bei diesem Apparat wird stets nur ein kleiner Teil der zu untersuchenden Flüssigkeit für sehr kurze Zeit einem hohen Strömungsgefälle ausgesetzt, während im Hauptteil der Flüssigkeit nur ein kleines Strömungsgefälle vorherrscht. Der Vorteil des Apparates besteht darin, dass ein hohes Strömungsgefälle zur Anwendung gelangen kann bei nur geringer Störung durch die bei hohem Strömungsgefälle eintretende Erwärmung der zu untersuchenden Flüssigkeit.
    Additional Material: 11 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 34 (1951), S. 1183-1202 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Les particules chargées d'un système quelconque contenant de telles particules, se répartissent d'une façon non homogène en présence d'un champ électrique. Dans le cas d'une solution aqueuse contenant des ions, les ions qui ne réagissent pas sur les électrodes (ions appelés inactifs) se répartissent selon le principe de Maxwell-Boltzmann.
    Additional Material: 7 Ill.
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In Part I the translational resistance of the random coil was discussed. In the two limiting cases of the freely draining and the completely nondraining coil a theoretical treatment was given, while for intermediate draining conditions an experimental method, involving large-scale models of the molecules, was shown to be available. The same treatment is now extended to deal with the analogous case of the hydrodynamic rotational resistance of the random coil. It is on this characteristic resistance that the intrinsic viscosity and the flow birefringence of solutions of chain molecules principally depend.Expressions are found for the viscosity index [η], the orientation index [ω], and the birefringence index [n], respectively. In these formulas Z is the degree of polymerization while the parameters aη, aη, aη, and brot are independent of Z. These parameters are, however, functions of the length Am of the preferential statistical chain element and the hydrodynamic thickness dh of the chain. an also includes the anisotropy of polarizability of the statistical chain element. It is seen moreover that [ω] (in contrast to [η] and [η]) also depends on the shape resistance of the chain (i.e., on the resistance which the chain inherently offers to a rapid change in configuration).
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 14 (1954), S. 193-208 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For the description of the practical properties of a large number of linear polymer molecules as well as for the discussion of the various mean parameters of the individual chain molecule, the model usually employed to represent the molecule consists of N m straight line chain elements of length A m statistically joined to each other (straight element model). For the construction of large-scale wire models of polymer molecules to be used in model experiments on the hydrodynamic behavior of chain molecules, a somewhat different model (circular segment model) was employed in previous papers. In these papers the relationships connecting the parameters which characterize these two models respectively have been determined on the basis of certain assumptions. These assumptions, as has recently been shown, were however partly in error and certain corrections have now to be applied to the numerical constants which appear in previously published formulas for the diffusion and sedimentation constants and for the intrinsic viscosity and streaming birefringence. The formulas, resulting after these corrections have been incorporated, are compiled in the present paper and the effect of these corrections on the interpretation of both new and old experimental results is discussed. It is found that agreement between theory and experiment is improved by the use of the corrected expressions and that in particular certain discrepancies which had previously existed between the lengths A m of the statistical chain element as calculated from sedimentation and diffusion experiments, on the one hand, and viscosity determinations on the other, disappear after these corrections are applied (see Table I).
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 65 (1982), S. 1655-1677 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isolation and Structure Determination of the New Cyclosporins E, F, G, H und IThe cyclosporins, a new group of biologically active metabolites, are produced by the fungus Tolypocladium inflatum GAMS (formerly designated as Trichoderma polysporum [LINK EX PERS.] RIFAI). They represent neutral cyclic oligopeptides composed of 11 amino acids. In addition to the already described cyclosporins A-D new minor compounds, cyclosporins E-I, have now been isolated from the crude cyclosporin-complex by applying extensive chromatographical separation procedures. The structures of the new compounds have been determined by spectroscopical evidence, hydrolytic cleavage and chemical correlation reactions as well as by X-ray analysis of suitable derivatives. Cyclosporins A, B, C, D and G differ from each other only in the nature of the amino acid no. 2. Cyclosporins E and I are N-demethylated congeners of cyclosporins A and D respectively, Cyclosporin F has been recognized as deoxycyclosporin A, whereas Cyclosporin H represents an epimeric form of cyclosporin A and contains N-methyl-D-valine in position 11.
    Additional Material: 10 Ill.
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gas phase emission and laser excitation spectra of the Ã2E↔X̃2E (Σ = +½, -½) transition of rotationally/vibrationally cooled 1-chloro- and 1-bromo-1,3-pentadiyne cations have been obtained. The emission was excited by electron impact on a seeded helium supersonic free jet and the fluorescence by laser excitation of cations produced by Penning ionization and collisional relaxation. From these two sets of data the origin bands of the spin-orbit systems are located and for the bromo species this leads to better values of the spin-orbit splitttings in the two electronic states and of the first adiabatic ionization energy. The vibrational frequencies of many of the fundamentals of these cations in the X̃2E and Ã2E states have been obtained to within ±2 cm-1.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 3025-3031 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Adducts of Lewis Acids with 1,2,4λ4,3,5-Trithiadiazole 1-OxideThe tittle compound 1 reacts with the Lewis acids SnCl4 and TiCl4 to yield the 2:1 adducts 1a and b and with AsF5 and SbF5 to form the 1:1 adducts 1c and d. According to the vibrational spectra and an X-ray analysis of 1a the coordination occurs via the oxygen atom. The ligands of 1a and b have cis-configuration. 1a crystallizes in the monoclinic space group P21.
    Notes: Die Titelverbindung 1 reagiert mit den Lewis-Säuren SnCL4 und TiCl4 zu den 2:1-Addukten 1a und b und mit AsF5 und SbF5 zu den 1:1-Addukten 1c und d. Nach den Schwingungsspektren und einer Röntgenstrukturanalyse von 1a erfolgt die Koordination über das Sauerstoffatom, und die Liganden in 1a und b haben cis-Konfiguration. 1a kristallisiert in der monoklinen Raumgruppe P21.
    Additional Material: 2 Ill.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Synthesis of a Spirocyclic Phosphoranide Anion: Model of an Intermediate in a SN2(P) ReactionIn an acid-base reaction the hydrophosphorane 9 reacts with triethylamine to give the spirocyclic phosphoranide 10, which is P-methylated by methyl iodide to form phosphorane 7 and O-silylated by trimethylsilyl iodide to form phosphite 12. The X-ray structure analysis of 10 shows a highly distorted trigonal bipyramide with the stereochemical active free electron pair in equatorial position. The difference in length of the axial P—O bonds is 0.25 Å. There is evidence for an equilibrium of 10 with the monocyclic phosphite alkoxide 10a in solution.
    Notes: Durch Säure-Base-Reaktion des Hydrophosphorans 9 mit Triethylamin entsteht das spirocyclische Phosphoranid 10, welches durch Methyliodid zu dem Phosphoran 7 P-methyliert und durch Trimethylsilyliodid zu dem Phosphit 12 O-silyliert wird. Die Röntgenstrukturanalyse von 10 ergibt eine stark verzerrte trigonale Bipyramide, in der das freie Elektronenpaar in äquatorialer Position sterisch wirksam wird. Die axialen P—O-Bindungen weisen einen Längenunterschied von 0.25 Å auf. In Lösung liegt 10 offenbar im Gleichgewicht mit dem monocyclischen Phosphitalkoxid 10a vor.
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