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Conformational properties of rigid-chain amphiphilic macromolecules: The phase diagram

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Abstract

The coil-globule transition in rigid-chain amphiphilic macromolecules was studied by means of computer simulation, and the phase diagrams for such molecules in the solvent quality-persistence length coordinates were constructed. It was shown that the type of phase diagram depends to a substantial extent on the degree of polymerization of a macromolecule. Relatively short amphiphilic macromolecules in the poor-solvent region always form a spherical globule, with the transition to this globule involving one or two intermediate conformations. These are the disk globule if the Kuhn segment is relatively large and the string of spherical micelles or the disk globule in the case of relative flexible chains. The phase diagram of a long rodlike amphiphilic chain turned out to be even more complex. Namely, three characteristic regions were distinguished in the region of a poor solvent, depending on the chain rigidity: the region of a cylindrical globule without certain order in the main chain, the region of the cylindrical globule with blobs having the collagen ordering of the chain, and the region of coexistence of collagen-like and toroidal globules. In the intermediate transitional region, not only conformations of strings of spherical micelle beads but also the necklace conformations in which the polymer chain in each bead has collagen ordering can occur in this case.

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Authors and Affiliations

  1. Faculty of Physics, Moscow State University, Leninskie gory, Moscow, 119992, Russia

    V. A. Markov & A. R. Khokhlov

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991, Russia

    V. V. Vasilevskaya, P. G. Khalatur & A. R. Khokhlov

  3. Department of Polymer Chemistry, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, Netherlands

    V. A. Markov & G. ten Brinke

Authors
  1. V. A. Markov
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  2. V. V. Vasilevskaya
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  3. P. G. Khalatur
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  4. G. ten Brinke
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  5. A. R. Khokhlov
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Correspondence to V. A. Markov.

Additional information

Original Russian Text © V.A. Markov, V.V. Vasilevskaya, P.G. Khalatur, G. ten Brinke, A.R. Khokhlov, 2008, published in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 6, pp. 965–976.

This work was supported by the Russian Foundation for Basic Research, project no. 05-03-33077; the Netherlands Organization for Scientific Research, project no. 047.011.2005.011; the basic research program of the Russian Academy of Sciences Division of Chemistry and Materials Science; and the National Scientific Research Center (CNRS), France.

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Markov, V.A., Vasilevskaya, V.V., Khalatur, P.G. et al. Conformational properties of rigid-chain amphiphilic macromolecules: The phase diagram. Polym. Sci. Ser. A 50, 621–629 (2008). https://doi.org/10.1134/S0965545X08060059

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  • DOI: https://doi.org/10.1134/S0965545X08060059

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