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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 817-832 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface potentials of monolayers of poly(methacrylic acid) (PMA) have been studied as a function of the pH of the subsolution. The influence of the macromolecular configuration on the properties of the ionizable groups was more particularly investigated. Orientation of molecules in the monolayer may be imposed by the stereoregularity of PMA (isotactic, atactic) and by the nature of the interface (air-water, cyclohexane-water). The results are analyzed in terms of theories of the ionic double layer (Gouy model, Donnan equilibrium) which permit the determination of the degree of ionization α of the film. The value of α gives indications about the orientation of specific groups of the macromolecular chain, i.e., of the ionized monomer units. Indeed, at the air-water interface, the film of isotactic PMA is more acid than that of the atactic sample, and at the cyclohexane-water interface, the degree of ionization is greater than at the air-water interface. These properties are the consequence of a modification of orientation of the hydrophilic groups with respect to the aqueous phase as a function of the stereoregularity of the sample and the nature of the interface. The variation of α with the pH of the substrate phase may be used to calculate an intrinsic dissociation constant Ks° of the molecules in the film. The value of Ks° is not modified by spreading conditions and remains very similar to that obtained in solution.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2125-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The validity of Silberberg's hypothesis concerning the conformation of branched polypeptides was tested by studies on solutions and on monolayers. The poly(α-amino acids) investigated consisted of poly-L-lysine backbones with side chains of poly(gamma;-benzyl L-gutamate) and poly(β-benzyl L-aspartate). In solution, the conformation was studied in the mixed solvent chloroform-dichloroacetic acid. Optical rotatory dispersion measurements demonstrated the existence of a helix-coil transition which is a function of the length of the side chain. A significant “transition curve” appeared between 9 and 15 residues. From the results, it may be assumed that the poly-L-lysine backbone is extended in a coiled conformation and the side chains are coiled or helical, depending on the number of glutamate residues. At the air-water interface, a discontinuity in the surface-pressure curve appears between 9 and 15 residues per side chain. The similarity with the results obtained in solution appears significant; however, this has to be confirmed with methods more specific for structural modifications.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase basicities of a series of cyclic and acyclic N-nitrosamines were determined by ion cyclotron resonance techniques. The fragmentation pattern and ion-molecule reactions of these compounds are discussed in terms of high resolution mass spectrometry and deuterium labeling. The presence of a unique rearrangement of the molecular ion is discussed in terms of specific ion-molecule proton transfer reactions and fragment ion products.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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