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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 361-375 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polysaccharide of salep orchid tuber was shown to be a glucomannan with a glucose/mannose ratio of 2.6 and an acetyl content of 2.1%. After extraction from the powdered root with water, the triacetate derivative was prepared and its configurational and hydrodynamic properties examined. The polymer yielded a series of fractions from 615 to 4170 in weight-average degree of polymerization. Light-scattering, viscosity, and osmometry experiments were conducted. Intrinsic viscosity results were interpreted according to the hydrodynamic theory of Eizner and Ptitsyn resulting in a value of ζ/η0 = 20 ± 6 A. for the ratio of monomeric friction coefficient to solvent viscosity and a corresponding value of a = 55 ± 4 A. for the persistence length, closely similar to those reported for other β-1,4-linked polysaccharides. The theoretical Flory coefficient increased with increasing molecular weight but was less than the limiting value of Φ0 = 2.86 × 1023 mole-1. The dependence of the light-scattering radius of gyration of the glucomannan polymer on the contour length showed that the configuration of the heteropolymer was similar to that of other β-1,4-linked polysaccharides which have only glucose or mannose in the main chain. Calculated radii of gyration based on the Porod-Kratky persistence length were found to be smaller than radii found by light scattering on the fractions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficients for the cellobiose through cellohexaose members of the cellodextrin series were determined in water. The molecular friction coefficients calculated on the basis of the Einstein diffusion equation can be represented by, ζN = N ζa + 2ζe, where ζa is the monomeric friction coefficient of an anhydroglucose unit, ζe is a friction coefficient assigned to a terminal monomer unit due to its additional hydrodynamic surface, and N is the degree of polymerization. For the cellodextrins, ζa is 1.25 × 10-9 dyne-sec./cm., and ζe is 2.42 × 10-9 dyne-sec./cm. The monomeric friction coefficient of the anhydroglucose unit was found to agree with the value calculated from literature data on the diffusion of cellulose in cadoxen. The calculations were based on the Ptitsyn-Eizner theory for the hydrodynamic behavior of the “wormlike” chain. The partial specific volumes of the cellodextrins were found to decrease from glucose to cellotriose and then to increase from cellotriose to cellohexaose.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 3 (1965), S. 1825-1832 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous results on the hydrodynamic and configurational properties of fully acetylated guaran in acetonitrile have been reexamined in light of the recent Eizner-Ptitsyn theory for the intrinsic viscosity of the semirigid macromolecule. Numerical values for the hydrodynamic function arising in the theory were calculated by numerical summation on an electronic computer and are tabulated. The theory is found to remove some of the inconsistencies inherent in earlier hydrodynamic theories and leads to reasonable values of the persistence length and monomeric friction coefficient of guaran acetate. The persistence length calculated from viscosity data was 57.8 A., only slightly lower than the limiting value of 64 A. obtained from light scattering. The ratio of monomeric friction coefficient to solvent viscosity was ζ/η0 = 6πr0 = 57.3 A., from which a value of r0 = 3.04 A. was obtained for the hydrodynamic radius of the monomer unit.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fully acetylated guaran, (guaran triacetate, GTA), was fractionated and the fractions in the weight-average degree of polymerization range of 171 to 12,400 were characterized by light scattering and viscometry. At high molecular weights, non-Newtonian flow was observed and after appropriate correction the intrinsic viscosity was found to be independent of shear gradient. Analysis of viscosity results according to the theory of Kurata and Yamakawa indicated that at high molecular weights the molecule is nondraining and that excluded volume effects are absent. Polymolecularity was estimated from ultracentrifuge and osmotic pressure measurements on certain key fractions and in the case of one fraction it was possible to determine the distribution of molecular weights and to demonstrate the validity of the Zimm-Schulz distribution. The ratio of the mean square radius of gyration to the molecular weight was found to decrease with increasing molecular weight indicating a non-Gaussian behavior that cannot be accounted for by the Porod-Kratky chain model. The dependence of radius of gyration on chain length is identical to that observed for hydroxyethyl cellulose and cellulose tricaproate indicating that the β-1,4-linked D-glucose chain of cellulose and the β-1,4-linked chain of GTA have similar configurations, in spite of chemical and structural differences between the anhydro sugar units. The α-1,6-linked D-galactose side groups on every other mannose unit of GTA do not appear to affect main chain configurations to any great extent. Equivalent bond lengths calculated from intrinsic viscosity and from light scattering indicate that it is necessary to distinguish between the hydrodynamic and light-scattering radius of gyration The Flory coefficient calculated from the light-scattering radius of gyration was found to increase with increasing molecular weight. When the hydrodynamic radius of gyration was used in the calculation, agreement with the theoretical Flory constant was within experimental error.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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