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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 30 (1958), S. 297-314 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this paper are presented new results obtained during further experimental and theoretical investigations of the form effect in the dynamic double refraction of polymers in solution. The use of the dumbbell theory of W. Kuhn for flexible chains in solution and of the optical modle of an equivalent ellipsoid for the macromolecule, permits the formulation of a theory of flow birefringence which takes account of the form effect for a wide range of shear rates. The conclusions of this theory are compared with new experimental data obtained in a study of polystyrene and p-tert-butylphenylmethacrylate in different solvents. In the range of low shear rates and concentrations, the theory is found to be in a good accord with experimental results. On the contrary, the study of the double refraction of several polystyrene fractions in dioxane in a wide range of shear rates and concentrations shows that macromolecules are less deformable in the flow than it follows from the dumbbell theory for ideally flexible chains. A new phenomenon was discovered experimentally - an anomalous dependence of the orientation angle on the shear rate of flow in the range of shear stresses at which the birefringence changes its sign because of compensation of the positive shape effect by the negative intrinsic anisotropy effect. Investigation of the concentration dependence of flow birefringence shows that this dependence is due to two causes - the hydrodynamic and optical interaction of the molecules. The optical interaction is characteristic only for those solutions in which the form effect takes place. A simple theory of concentration dependence of the form effect is proposed which is in good accordance with experimental data.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 16 (1979), S. 847-855 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The investigation of the factors determining the formation and stability of the higher biopolymers structures is one of the most important trends of the development of molecular biophysics. A feature common to most macromolecular systems under physiological conditions is that they function in an aqueous environment. Thus, it is natural to assume that the peculiarities of biological macromolecules structures and their functional activity as well are closely related to the specific properties of such a unique solvent as water. The investigations of the conformational changes of biopolymer, induced by dehydration of the macromolecule, give information about the nature of the forces stabilizing its structure. The dehydration of the macromolecule in solution can be attained by addition of a nonaqueous cosolvent. Generally low-molecular-weight aliphatic alcohols, amides, and amines are used as a nonaqueous component. At present a vast number of experimental and theoretical data concerning the properties of water and aqueous systems are available. The specificity of water as a solvent arises primarily from the spatial hydrogen-bonded structure. The addition of a nonaqueous component exerts changes in this structure, which evolve to the singularities of the physical characteristics of water-nonelectrolyte mixtures. It is generally assumed that nonelectrolytes may be divided, according to their effect on the spatial water structure, largely into two basic classes: (1) the structure makers, i.e., the compounds of aliphatic alcohols type; (2) the structure breakers, i.e., the compounds of urea type. The agents belonging to the first class show a stabilizing effect in the range of low nonelectrolyte content. At a certain critical concentration, Ccrit, characteristic of each substance, the nonaqueous solute molecules leave the cavities of the spatial water structure which leads to a disruption of the latter. The agents belonging to the second class exert a structure-breaking effect even in the range of extremely low concentrations, which arises from their high competitive ability for hydrogen bonding.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of alcohol-water solvents on the conformation of native DNA was studied by the methods of flow birefrigence and viscometry. Conformational transitions of DNA were observed at low alcohol concentrations corresponding to the destruction of the water spatial structure. A change in the secondary structure of the DNA molecule was observed at high ethanol concentrations and is discussed in the paper.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of deoxyribonucleoprotein (DNP) from calf thymus at different stages of deproteinization was studied.The dissociation of the first portion of histone produces no effect on the hydrodynamical and optical behavior of DNP particles. The conformational transition of a macromolecule was observed as soon as the ratio of protein to DNA ≤ 0.9.The effect of ionic strength on the conformation of DNP particles with high protein content was more strongly pronounced than that for DNA. On the contrary, DNP particles depleted of proteins (protein/DNA 〈 0.9) were found to be less sensitive than DNA to the variation of ionic strength. These data imply that the DNP molecules rich in proteins possess a superstructure that is destroyed as the protein/DNA ratio becomes 0.9.The data were analyzed in view of current theories on various model concepts. The most probable model to describe the DNP molecule was chosen by comparing the calculated and experimentally obtained parameters. We believe that DNP is best described as a “compressed coil,” possibly including superhelical regions.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 13 (1974), S. 2077-2085 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation behaviour of DNP samples from calf thymus partially depleted of protein was studied. Upon transition from DNP to DNA a twofold decrease of the sedimentation constant, S02 0,W was observed. The translational friction coefficient f of DNP calculated from S02 0,W does not change at deproteinization, whereas the intrinsic viscosity [η] increases notably. Such difference in the dependence of f and [η] on the protein content is interpreted in terms of the theories for semirigid coils. The application of different models of DNP structure for the description of the hydrodynamic behaviour of DNP is considered. A model of the semirigid coil formed by a DNP chain partly folded into the superhelix seems to be most preferable.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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