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  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton magnetic resonance data have been obtained for 6-methyl-2′-deoxyuridine (dT*), its 3′- and 5′-monophosphates, and its 3′,5′-diphosphate, as well as for the corresponding thymine derivatives. The synthesis of the dideoxynucleoside monophosphates - d(TpT), d(T*pT), d(TpT*), and d(T*pT*) - was accomplished, and spectral data were obtained for these four dimers. The data show that the 6-methyluracil base prefers the syn conformation about the N-glycosyl bond at the monomer and dimer levels. The presence of the syn base leads to increases in the cis couplings of the sugar ring, J1′2″ and J2′3′, which indicate a trend towards eclipsing of the substituents on the C1′-C2′ and C2′-C3′ fragments. This trend is discussed in terms of changes in the pseudorotational parameters which describe the pucker of the ring. The syn base destabilizes the g+ conformer about the C4′-C5′ bond, leading to a preference for the t conformer in all dT* residues at the monomer and dimer levels. Preliminary work on the formation of cyclobutane-type photodimers in d(T*pT) and d(T*pT*) is discussed and presented as evidence for the capability of the syn 6-methyluracil base to form base-stacked complexes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The geminal and vicinal 13C-31P coupling constants have been monitored, as a function of pH, for a series of uracil and cytosine 3′- and 5′-nucleotides with a ribose, arabinose, or 2′-deoxyribose sugar. Data were also obtained for two 3′,5′-diphosphates in the ribose and arabinose series. The geminal J(C5′-P5′) and J(C3′-P3′) couplings show only a small dependence on the ionization state of the phosphate, decreasing by 〈 0.5 Hz in the pH 5-7 range. For the ribose and arabinose 3′-nucleotides, the vicinal J(C4′-P3′) increase (up to 1.5 Hz) on secondary phosphate ionization in the pH 5-7 range, whereas their J(C2′-P3′) couplings decrease (up to 1.5 Hz) over the same pH range. In contrast for the 2′-deoxyribose molecules, both couplings decrease (∼0.5 Hz) on phosphate ionization. The titration curves provide information about the influence of the sugar on the conformation about the C3′—O3′ bond. Some conformational trends could be rationalized by consideration of the sugar-puckerdependent contact interactions between the 3′-phosphate and the substituents on the furanose ring.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 191-201 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of crystallinity and radiation crosslinking on the water induced depression of the glass transition temperature in Nylon 4 [poly(2-pyrrolidone)] has been investigated by differential scanning calorimetry. Radiation crosslinking was effective in preventing exothermic events associated with crystallization during the measurement of the incremental change in heat capacity (ΔCp); a parameter necessary for the theoretical evaluation of the depressed glass transition temperature. ΔCp, when normalized to account for fractional crystallinity, was found to deviate substantially from a linear two phase relation. A simple three phase representation of morphology is proposed to account for this deviation, and assumptions have been made regarding the distribution of plasticizer, leading to good agreement between the theoretical and experimentally observed depressions of the glass transition temperature.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystalline structure and the melting behavior of vinylidene fluoride/vinyl fluoride (VF) copolymers are reexamined. For copolymers containing even a small mole fraction of VF units (≍ 12%) a structure similar to the β-form of poly(vinylidene fluoride) and to the crystalline structure of poly(vinyl fluoride) is stabilized. Combined wide-angle X-ray scattering, differential scanning calorimetry and dielectric measurements show that in contrast to other vinylidene fluoride copolymers, no crystal-crystal transition below the melting region is present.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Kinetic data are reported for the fast polymerization of a thermoplastic polyurethane under conditions similar to that of commercial reaction injection molding (RIM). The components were a 2000 molecular weight polyester polyol, butanediol and 4,4′-diphenylmethane diisocyanate. Three catalysts-dibutyltin dilaurate, phenyl mercuric propionate, and triethylenediamine-as well as uncatalyzed formulations were studied. Kinetic parameters were obtained by numerically fitting adiabatic temperature rise data with both second-order and hyperbolic models. The hyperbolic model gave consistently better fits and is supported by mechanistic studies in the literature. Activation energies compare well to literature values. The uncatalyzed rate was found to be significant. The kinetic parameters obtained by this method are useful measures of catalyst performance in the RIM systems. Moreover, the models provide a conveient way to predict the extent of reaction during the production of parts by the RIM process. The shape of the reaction pathway (extent of reaction time) may be important in the development of physical properties of polymers produced by the RIM process. Physical properties for these samples compare favorably to those for a conventionally produced (batch) polyurethane of the same formulation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 679-693 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The analysis of dielectric loss data is frequently complicated by the presence of ohmic conductivity, especially at lower frequencies. Two simple methods are discussed for locating transition temperatures and for determining activation energies in such cases. In the first method the permittivity derivative [dε′(T)/dT] is used; in the second, permittivity difference spectra ε′(T, v1) - ε′(T, v2) (v1 ≪ v2 are used. The latter technique, however, cannot be used for activation energy determination. The theoretical basis of these methodologies and an analysis of representative experimental data are presented. The data set include measurements of pure and filled polyurethanes and of radiation-cured unsaturated polyester resins. Finally, the advantages of data presentation in the form of ε′ and ε″ instead of tan δ are discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 36 (1988), S. 243-248 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 26 (1988), S. 3241-3249 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new types of p-xylene bis-sulfonium chloride monomers were prepared from cycloalkylene sulfides. The polymerization characteristics of these monomers to form poly(p-xylene sulfonium chlorides), and the thermal elimination reactions of their polymers to poly(p-phenylene vinylene), were compared with those of two monomers prepared from dialkyl sulfides. The cycloalkylene sulfonium chloride monomer polymerized to higher yields and to higher molecular weight polymers, which showed more efficient elimination reactions.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 2345-2357 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of pressure on the miscibility of blends of poly(2,6-dimethyl-l,4-phenylene oxide) (PPO) with a random copolymer of styrene and para-fluorostyrene, P(S-co-p-FS), has been studied by high pressure differential thermal analysis (HPDTA). P(S-co-p-FS) copolymers less than 36 mole % p-FS are miscible with PPO in all proportions irrespective of pressure up to 200 MPa, using the customary criterion of a single calorimetric glass relaxation. P(S-co-p-FS) copolymers containing 40 to 50 mole % p-FS undergo phase separation upon annealing at elevated temperatures, indicating the existence of a lower critical solution temperature (LCST). In these blends, pressure displaces the phase boundary associated with the LCST to higher temperatures causing an apparent increase in polymer miscibility. The phase diagram for the blend of PPO and P(S-co-p-FS) containing 46 mole % p-FS, shows that the critical composition at about 50 wt % PPO does not change with pressure, but the consolute temperature Tc increases with increasing pressure. The pressure dependence of the LCST (dTc/dP) of this system is about 0.35°C/MPa.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 2793-2804 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron diffraction patterns of highly oriented poly(p-phenylene vinylene) films obtained by the soluble polymeric precursor route are interpreted on the basis of a monoclinic unit cell containing two monomer units: c (chain axis) = 0.658 nm, a = 0.790 nm, b = 0.605 nm, α ≃ 123°. The molecules are nearly perfectly oriented along the stretching direction but exhibit partial axial translational disorder.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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