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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 12 (1973), S. 2335-2349 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of poly dispersity on the nuclear magnetic resonance spectra of samples of poly-γ-benzyl-L-glutamateein the helix-random coil transition is studied. In the transitionregion the α-CH proton resonance shows two peaks whose behavior does not change appreciably upon fractionation by gel permeation chromatography. Theoretical spectra were computed with both a polydispersity model of the transition and a model for slow nucleationof helix from completely random coil molecules. The results suggest that the double peak behavior in the nmr spectra results from a slow rate of helix nucleation rather than polydispersity.
    Additional Material: 9 Ill.
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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 determination of the conformation of a cyclic heptadecapeptide derived from the second loop of human transforming growth factor-α, [Ala21]-hTGF-α-(16-32), is described. Two-dimensional homonuclear Hartmann-Hahn and rotating-frame cross-relaxation spectroscopy in H2O were used to obtain the complete proton resonance assignments and the necessary distance constraints between nonbonded hydrogen atoms to derive a conformation without involving any energy minimization. The result is an ellipsoidal-shaped structure with a turn at Gly19 and a bend formed by residues 26-29, Gln-Glu-Asp-Lys. Comparison is made with the second loop of human epidermal growth factor and the results are discussed in terms of receptor binding and biological activity.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 7 (1969), S. 155-171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance spectra at 100 MHz and 220 MHz have been obtained on two samples of poly-L-alanine of differing molecular weights (2500 and 42 500) in the chloroform-trifluoroacetic acid system under various conditions of solvent composition, temperature, and polypeptide concentration. Separate helix and random coil peaks are observed for the α-CH and peptide NH backbone proton resonances, thereby permitting the determination of helix content. This observation of separate peaks demonstrates that the lifetimes of the helix and random coil portions of poly-L-alanine have lower limits of about 10-1 sec. It is suggested that solvent-peptide versus peptide-peptide hydrogen bond competition, coupled with a destabilizing effect of the trifluoroacetic acid on the helix, is responsible for the helix-random coil transformation.
    Additional Material: 12 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2575-2578 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interactions of meso-tetra(4-N-methylpyridyl)porphyrin [TMpyP(4)], meso-tetra(2-N-methylpyridyl)porphyrin [TMpyP(2)], and meso-tetra(para-N-trimethylanilinium)porphyrin (TMAP) with several native and synthetic DNAs were studied by a variety of physical techniques: nmr (31P and 1H), absorption spectroscopy, viscosity, and flow dichroism (FD). Of the three porphyrins studied, only the interaction of TMpyP(4) with poly [d(G-C)2] was fully consistent with intercalation. In particular, a large increase in viscosity, a downfield 31P-nmr signal (ca. -1 ppm), and upfield imino proton signals (11 to 12 ppm range) were observed. Comparison of the effects of TMpyP(4) on DNAs of different GC contents revealed larger changes in solution viscosity with increased GC content. However, the characteristic changes in 31P- and 1H-nmr spectra were not observed. The viscosity increases observed in studies with poly[d(A-C)(G-T)] and C. Perf. DNA were much lower than with poly[d(G-C)2], M. Lys. DNA, and calf thymus DNA. Thus, GC sequence and content are clearly important. The principal change in the 31P-nmr signal of native DNA is the appearance of a very broad shoulder centered at ca. -2.0 ppm, which is larger in M. Lys. DNA than in C. Perf. DNA. FD studies indicate highly ordered TMpyP(4) cations arranged perpendicular to the DNA axis of calf thymus DNA. Together, these results suggest the major effects of TMpyP(4) on DNA properties are due to strong GC-binding interactions that influence DNA structure. The data are consistent with combined intercalative and outside binding interactions of TMpyP(4) with GC regions of DNA. In contrast, similar studies with TMAP suggest that it influences AT regions of DNA by an outside binding mode. On the other hand, TMpyP(2) effects on DNA properties are consistent with nonselective outside binding.
    Additional Material: 11 Ill.
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  • 6
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed description of the two observed solution conformations of the pentapeptide lactone fragment of actinomycin D is presented using the distance constraints obtained from two-dimensional nuclear Overhauser enchancement spectra in combination with minimum energy calculations. Low energy conformational states that are compatible with the experimental distances are found for each of the two conformers. For one conformer, an all trans peptide bond conformation is found with no intramolecular hydrogen bonds. For the other conformer, the D-Val-Pro and Pro-Sar peptide bonds were cis; this solution conformation is the same as that found in both the crystal structure of the pentapeptide lactone as well as of the native actinomycin D itself. These results are discussed in terms of the combined influence of conformation and the effects of mutual intramolecular association of the pentapeptide lactone moieties in native actinomycin D on its cytotoxic activity.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 2097-2116 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical stress relaxation of two polyurethane elastomers Genthane S and Adiprene CM has been studied in air and in nitrogen in the temperature range 60 to 150°C. Both continuous and intermittent stress relaxation measurements were made on well characterized samples covering a range of crosslink densities. Scission and crosslinking reactions were observed for both the polyester based Genthane S and the polyether based Adiprene CM. The degradation of Genthane S is largely non oxidative and the scission reaction involves the main chain. The behaviour of Adiprene CM under nitrogen broadly resembles that of Genthane S; it differs from Genthane S in that it also undergoes an oxidative reaction. Activation energies for the scission and crosslinking processes were evaluated from kinetic analysis. Pretreatment of the elastomers with isocyanates inhibits both of these reactions. A mechanism involving the urethane group is proposed to account for the degradation behaviour and the role of water in this respect is discussed briefly.
    Additional Material: 14 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 725-731 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An unsaturated segmented polyurethane was prepared from cis-2-butene-1,4-diol, poly(ethylene glycol), butane-1,4-diol, and methylene bis(4-phenyl isocyanate). Graft copolymerization of N-vinylpyrrolidone onto the segmented polyurethane was studied using 2,2′-azoisobutyronitrile (AIBN) as initiator in DMF as solvent. The graft copolymers were isolated from the homopolymer and the ungrafted polyurethane by selective solvent extraction. The effect of reaction time, temperature, and of monomer and initiator concentrations on the degree of grafting was also investigated. The percent grafting was enhanced with increasing [AIBN] up to 40 mmol.dm-3, but then decreased at higher concentrations. An explanation based on complex formation between the monomer and the urethane linkages in polyurethane is suggested.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 675-685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength and extensibility of an unfilled styrene-butadiene rubber vulcanizate were determined in constrained biaxial tension (essentially pure shear) by stretching thinwalled cylindrical specimens in the axial direction with an Instron tester while gas pressure was admitted to maintain constant the outside diameter of a specimen. The rupture stress, λ1b, and the extension ratio, λ1b, in the axial direction and the rupture stress, σ2b, in the circumferential direction were determined at extension rates from 0.0031 to 3.1 min-1 and temperatures from 25 to 90°C. Rupture data in simple tension were also obtained by testing ring specimens under similar test conditions. The time-temperature shift factor, aT, obtained by superposing rupture data at different temperatures, gives a constant activation energy of 35 kcal. Doubly logarithmic plots were prepared showing the dependence of σ1b/λ1b, σ2b, and λ1b from the biaxial tensile tests and of σb/λb and λb from the simple tensile tests on the temperature-reduced extension rate, \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. (The quantities σ1b/λ1b, σ2b, and σb/λb are rupture stresses based on the dimensions of undeformed specimens.) At equal values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}, the extension ratios λ1b and λb are sensibly identical. The ratios σ1b/σb and σ2b/σb, as well as λbσ2b/σb, were obtained from rupture data read from the composite curves at selected values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. Also, similar ratios were derived from stress data at equal extensions in biaxial and simple tension for 1.25 ≤ λ ≤ 3.0, the range comparable to that in which rupture data were obtained. A consideration of the ratios given by both the rupture and the stress data shows that the von Mises failure criterion is not applicable, although the departure is small except at the larger values of λb.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 24 (1986), S. 519-528 
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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