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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 379-389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper extends a previous study in which a discontinuity in the specific rotation of open chain α-l,4-linked glucopyranosides in the water-dimethyl sulfoxide (H2O-DMSO) system was attributed to a symmetry change about a polymer chain segment. Optical rotation of amylose, cyclohexamylose, methyl β-maltoside, and dextran was measured in the following mixed solvent systems: formamide-dimethyl sulfoxide (F-DMSO), ethylenediamine-dimethyl sulfoxide (E-DMSO), and hexamethylphosphoramide-dimethyl sulfoxide (HMPA-DMSO). Refractive index measurements were used in an attempt to detect hydrogen bonding between solvent components. The specific rotation of amylose corrected for variation in refractive index (CSR), as a function of solvent composition, showed a discontinuity at solvent compositions corresponding to about 1 mole F to 2 moles DMSO and to 1 mole E to at least 8 moles DMSO. A discontinuity in the CSR function of amylose in the H2O-DMSO mixed solvent that occurs at 25°C is not observed at 70°C. The CSR function of methyl-β-maltoside exhibits a discontinuity in solvent composition corresponding to mole ratios between 2F-DMSO and 3F-DMSO. Present results indicate that an amylose chain segment may undergo a symmetry change in solvent compositions corresponding to mole ratios between F-DMSO and F-2DMSO. Our CSR measurements of amylose and model compounds in E-DMSO and HMPA-DMSO do not permit us to distinguish between possible changes in amylose chain segment symmetry and solvent interactions that could affect symmetry properties of the glucopyranose ring.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dextran produced by Leuconostoc mesenteroides NRRL B-512 was acid-hydrolyzed and fractionated, yielding a series of fractions from which 24 were selected that ranged in molecular weight from 17,700 to 9.5 million. Light-scattering and viscosity measurements were made on all fractions, and selected fractions were characterized by endgroup determinations and velocity ultracentrifuge measurements. Branching in these dextran fractions was evidenced by the progressively decreasing slope of the curve of logarithm of intrinsic viscosity plotted against logarithm of molecular weight, attaining a value of 0.11 at M = 107; by the upward curvature of the log-log plot of sedimentation constant against molecular weight; and by the relatively large values of k′ in the Huggins specific-viscosity equation for the high-molecular fractions. Assuming Lansing-Kraemer molecular-weight distributions for the dextran fractions and using sedimentation data to furnish β, the measure of breadth of the distributions, physical characterizations were corrected for polydispersity. For molecular weights below 100,000, [η] = 1.0 × 10-3 Mv0.50. In the range 18,000 〈 M 〈 400,000 S200 = 0.0251 M00.44. The constant Φ′, of the Flory-Fox theory, corrected for polydispersity of the fractions, was found to be 55.2 × 1021, which is larger than the value reported for linear polymers. It is concluded that the ratio of root-mean-square radius and hydrodynamic radius effective in viscosity differs for branched and linear molecules. The quotient (Φ′)1/2/P′ also appears to be significantly smaller for dextran than the value reported for linear molecules. Increase in Φ′, for dextran above the value previously assumed necessitates recalculation of data of Wales, Marshall, and Weissberg for g, the ratio of mean-square radii of branched and unbranched dextran molecules.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 22 (1991), S. 111-117 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Visible excitation resonance Raman difference spectra, in resonance with the 605-nm absorption maximum of fully reduced and mixed-valence cyanide-bound cytochrome oxidase, were recorded. Under these conditions, the vibrations of ferrocytochrome a are markedly enhanced owing to its dominant contribution to the 605-nm α-band absorption of reduced cytochrome oxidase. The effect of H/D exchange in the Raman spectra of cytochrome a was also investigated as a way to establish formyl- and vinyl-peripheral substituent sensitive modes. Measurements of the depolarization ratio dependence of cytochrome a vibrational modes resulted in some isotope-sensitive modes with characteristic depolarized behavior; however, it was observed that the majority of the visible excitation vibrations exhibit polarized values. This is interpreted as being due to a significant lowering in the molecular symmetry of the heme a porphyrin macrocycle caused by the unusual peripheral substituent pattern of heme a and, presumably, by the strong cytochrome a-protein interactions. Both structural effects appear to result in a selective enhancement of cytochrome a Eu substituent-sensitive modes as detected by the low-frequency resonance Raman spectrum.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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