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  • Polymer and Materials Science  (15)
  • Life and Medical Sciences  (5)
  • yellowfin tuna  (3)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 18 (1979), S. 609-623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general model for the large-scale, time-independent structure of duplex DNA is developed based on elastic considerations. The general conditions of elastic equilibrium are given. These equations are solved for the equilibrium shape of stressed duplex DNA, based on the assumption that the double helix behaves mechanically as a symmetric, linearly elastic rod. It is shown that, in general, two orders of superhelicity will arise at equilibrium. Several possible applications of this approach to the supercoiling of closed circular DNA are described.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 2143-2164 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theoretical kinetics are analyzed for reactions between torsionally stressed DNA and another compound which reacts at different rates with portions of the substrate molecule which are in different conformational states. These reactions are assumed to obey Michaelis-Menten kinetics, so no cooperative effects occur. The DNA is regarded as being susceptible to a stress-induced local conformational transition as described recently by Benham. Briefly, alterations in torsional stress consequent on superhelicity effectively change the relative concentrations of the two conformational states of the substrate, thereby influencing the course of the reaction. This theory is developed for transition between the B-form helix and the single-stranded, random-coil states. To illustrate the influence of posited stress-induced melting on kinetics, calculations are made on simple models of two biochemical phenomena. First, the variations in initial nicking rates of single-strand-specific endonucleases with substrate superhelicity are interpreted as arising from changes in the concentration of (stress-induced) single-stranded binding sites. Second, the observed dependence of the transcription rate of RNA polymerase core enzyme on substrate superhelicity is interpreted in terms of a model in which the rate-limiting step in the initiation event is the formation of a complex between the enzyme and a single-stranded region. Related experimental results are shown to be qualitatively consistent with the suggestion that sufficiently supercoiled DNA contains locally melted regions.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 22 (1983), S. 2477-2495 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper analyzes the elastic equilibrium conformations of duplex DNA constrained by the constancy of its molecular linking number, Lk. The DNA is regarded as having the mechanical properties of a homogeneous, linearly elastic substance with symmetric cross section. Integral representations of the writhing number Wr and of Lk are developed, in terms of which the equilibria are given as solutions to an isoperimetric problem. It is shown that the Euler angles defining equilibrium conformations must obey equations identical to those governing unconstrained equilibria. A scaling law is developed stating that molecules supercoiled the same amount ΔLk will have geometrically similar elastic equilibria regardless of their length. Thus, comparisons among molecules of properties related to their large-scale tertiary structure should be referred to differences in ΔLk rather than to their superhelix densities. Specific conditions on the elastic equilibrium conformations are developed that are necessary for ring closure. The equilibrium superhelical conformations accessible to closed-ring molecules are shown to approximate toroidal helices. Questions relating to the stability and nonuniqueness of equilibria are treated briefly. A comparison is made between these toroidal conformations and interwound configurations, which are shown to be stable, although they are not equilibria in the present sense. It is suggested that entropic factors are responsible for favouring the toroidal conformation in solution.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 26 (1987), S. 9-15 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2793-2798 
    ISSN: 0887-624X
    Keywords: highly branched radial block copolymers ; dendritic initiation ; alipatic polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Living ring opening polymerization of ε-caprolactone initiated from the numerous chain-end hydroxymethyl groups of the analogous dendrimeric and hyperbranched polyesters derived from 2,2-bis(hydroxymethyl) propionic acid is described. By controlling the size of the dendritic macromolecule and the molar ratio of ε-caprolactone, a variety of highly branched radial block copolymers are obtained. Comparison of the results obtained for the dendrimeric and hyperbranched initiators demonstrates that the reactivity of the chain-end hydroxymethyl groups in the dendrimer are significantly greater than in the isomeric hyperbranched case. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2793-2798, 1998
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2161-2167 
    ISSN: 0887-624X
    Keywords: alkoxyamine ; living free radical polymerizations ; asymmetric epoxidation ; Jacobsen's catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 1 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1627-1633 
    ISSN: 0887-624X
    Keywords: hyperbranched macromolecule ; polyester ; focal point groups ; intramolecular cyclization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of monomer structure and catalyst on the synthesis of hyperbranched polyesters based on 4,4-(4′-hydroxyphenyl)pentanoic acid has been examined. The nature of the ester group and the catalyst have a significant effect on the molecular weight of the hyperbranched polyester but do not effect the degree of branching for these materials. The fate of the single ester group at the focal point of these hyperbranched macromolecules is probed by the synthesis and polymerization of 13C labeled methyl 4,4-(4′-hydroxyphenyl)pentanoate. Comparison of the molecular weights determined by 1H- or 13C-NMR spectra with those determined by osmometry suggest that intramolecular cyclization does not occur to a significant extent in these systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1627-1633, 1997
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 679-696 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper analyzes equilibrium superhelical cruciform formation in a topologial domain of DNA containing inverted repeat sequences. The cruciform conformation is shown to be stable when the molecule is sufficiently negatively supercoiled but not when it is positively supercoiled. For a particular sequence containing a single inverted repeat, onset of stability occurs at a degree of negative superhelicity that depends critically on the number of base pairs separating the repeat copies. The free energy associated with the stable cruciform state is constant, independent of the degree of superhelicity, up to the point where the complete inverted repeat participates in the cruciform. In contrast, the free energy of the alternative, unextruded state grows approximately quadratically with the superhelical deformation. Therefore, a degree of negative supercoiling occurs at which the cruciform state becomes energetically favored. The equilibrium properties of this cruciform extrusion transition vary with segment length, the positions and sizes of the inverted repeats involved, environmental conditions, and the degree of superhelicity imposed. In a segment containing multiple repeats, both tandem and inverted, of one or more sequences, the pattern of cruciforms that form is dependent on superhelicity in a complex way. Specific cruciforms may occur at equilibrium only in narrow ranges of superhelicity, their reabsorption being coupled to the extrusion of others.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2247-2259 
    ISSN: 0887-6266
    Keywords: glass transition temperature ; polymer ; repeat unit ; correlation ; structure ; rotational degrees of freedom ; topology ; copolymerization ; crosslinking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The empirical form for the dependence, Tg(n) ≅ Tg(∞)·(1 + α/n), of the glass transition temperature Tg on the average number n of repeat units between crosslinks, is generalized for randomly crosslinked high polymers. The new form, Tg(n) ≅ Tg(∞) · [1 + c/(n·Nrot)], is based on a correlation study of data for 77 samples of 10 different sets of resins. The fitting parameter α is resolved into composition-dependent Nrot and composition-independent c terms. Nrot summarizes the average number of rotational degrees of freedom per repeat unit, and is estimated in a straightforward manner from the structure and mol fraction of each repeat unit. The value of c is found from data analysis to be 5 ± 2. The results of this work are consistent with expectations based on the entropy theory of glasses, and provide improved understanding and predictive ability for the properties of crosslinked polymers. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 10
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Well defined graft copolymers have been synthesized by a nitroxide-mediated “living” free radical process using pre-formed macromonomers. Analysis of the graft systems revealed that the macromonomer was efficiently incorporated into the polymeric backbone to give block copolymers of controlled molecular weight and narrow polydispersities. An added benefit of the “living” free radical process is that macromonomers, such as polylactide or polycaprolactone, which contain reactive functional groups can be used to form novel graft systems using this approach. Functionalized monomers or polymeric initiators were also used in the copolymerization mixture to give graft systems with a variety of functional groups attached to the backbone.
    Additional Material: 4 Ill.
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