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  • 1
    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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  • 2
    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.
    Type of Medium: Electronic Resource
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  • 3
    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.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 923-935 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of nitroxide-mediated ‘living’ free radical procedures as a synthetic tool for obtaining polymers with well defined and complex macromolecular architectures is discussed. The preparation of linear homo, block, and random co-polymers by ‘living’ free radical procedures have been demonstrated for a variety of systems and results in a significant increase in control over the macromolecular structure when compared to traditional free radical polymerization. The factors which affect the success of this novel synthetic approach will be reviewed and the advantages of ‘living’ free radical polymerization over other living polymerization techniques discussed. The synthesis and chemical stability of a wide range of unimolecular alkoxyamine initiators will also be demonstrated and their use in the preparation of complex macromolecular architectures such as hyperbranched polymers and hybrid dendritic-linear polymers illustrated.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 259-264 
    ISSN: 0887-6266
    Keywords: liquid crystalline polymer solutions, MWD from viscometry in ; cis-Polybenzoxazole/polyphosphoric acid, MWD from viscometry liquid of, crystalline solutions of ; intrinsic viscosity and MWD in dilute solutions of rodlike liquid crystalline polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight for a dilute solution of cis-polybenzoxazole (PBO) in polyphosphoric acid (PPA) was determined by fitting the rheological data with a semiempirical polydisperse hybrid theory. The hybrid theory models a semiflexible rigid rod as an elastic cylinder. The cylinder has both a rotational relaxation spectrum given by an ideal rigid rod and an internal bending relaxation spectrum spaced in accord with the relaxation time spectra of a flexible coil with fully developed hydrodynamic interactions. The model was fitted to rheological data collected for a 0.05 weight percent solution with intrinsic velocity (one-point determination) of 320 ± 10 cc/g. The model predicts a number-average molecular weight near 12800 ± 400 g/mol with a polydispersity index of 2.5 ± 0.1. By using the Yamakawa-Yoshizaki equation the intrinsic viscosity is calculated for the model molecular weight distribution as 310 cc/g.
    Additional Material: 2 Ill.
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  • 6
    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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  • 7
    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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  • 8
    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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  • 9
    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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  • 10
    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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