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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 579-588 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding of the cationic dye auramine O (AuO) to the polysoap-type polymers poly(vinylbenzo-18-crown-6) (P18C6) and polyvinylbenzoglyme (PVBG) in water were studied by fluorimetry and dialysis. The quantum yield of P18C6-bound AuO was found to be 0.028, the value being 0.018 for AuO bound to PVBG. The intrinsic binding constants were found to be 2.2 × 104M-1 (P18C6) and 1.2 × 104M-1 (PVBG), the respective first binding constants being 317 and 63M-1. Addition of crown-ether-complexable cations such as K+, Tl+, or Cs+ converts the neutral poly(crown ether) into a polycation, causing repulsion of the cationic dye and a strong decrease in the AuO fluorescence. AuO fluorescence was also studied in the absence of polymer in ether solvents, giving θ values of 0.011 and 0.018 in THF and dioxane. Traces of water rapidly form a nonfluorescent species. Solutions of AuO in water without polymer present exhibit very strong fluorescence on addition of BPh4 anions owing to formation of AuO+, BPh4- ion pairs and higher aggregates.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3001-3010 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of 41-(1-pyrenyl)butyltrimethylammonium bromide (PN+) to the neutral poly-soap-type polymers poly(vinylbenzo-18-crown-6) (P18C6) and poly(vinylbenzoglyme) (PVBG) was studied by optical spectroscopy and fluorescence in the presence and absence of salts. Measurements of the respective binding constants were based on distinct differences in the optical absorption spectra of free and polymer-bound PN+. When crown ether-compelxable cations (e.g., K+) were added the adsorption of PN+ to P18C6 decreased as the neutral polymer was converted to a polycation. No decrease was found with PVBG because alkali ions do not complex significantly to this polymer in water. PN+ adsorption to both polymers rose rapidly, however, as the salt concentration increased. This effect was strongly anion-dependent and increased in the order of Cl- 〈 Br- 〈 I- 〈 CNS- 〈 BPh4-. The increased binding was reflected in a higher binding constant and also in a larger number of bound PN+ molecules per polymer chain under saturation conditions. It is argued that the formation of ion pairs or larger ion clusters in the aqueous phase when anions are added forces more PN+ molecules to adsorb on the surface of the polymer coil to which they are bound as ion pairs or higher aggregates. Under saturation conditions enough PN+ molecules are bound to convert the pyrene monomer fluorescence spectrum into that of the excimer. These results are compared with data obtained for the anionic solute 4-(1-pyrenyl)butanoate in the presence of salts.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1629-1638 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Insoluble complexes are formed in acidic aqueous media when poly(acrylic acid) (PAA) and poly-(vinylbenzo-18-crown-6) (P18C6) or polyvinylbenzoglymes are mixed. Complex formation results from hydrogen bonding between carboxyl groups and crown ether- or glyme-oxygen atoms as well as from hydrophobic interactions. The precipitation is pH dependent and was determined as a function of the ratio PAA to P18C6 or to polyglyme at different HCl concentrations in 10-4M solutions of polycrown or polyglyme. Precipitation is nearly quantitative in 0.01N HCl. The compositions of PAA/P18C6 precipitates were determined as a function of the initial PAA/P18C6 ratio in solution. The complexes with P18C6 can be solubilized in acidic media when crown-complexable cations (K+, Cs+, Ba2+) are added, but the charged P18C6 reprecipitates in basic solution as a polysalt complex with the PAA-polyanion. More stable PAA-P18C6 complexes in the form of fibers can be obtained by interfacial complex formation. Poly(methacrylic acid) is less effective as a complex former.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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