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Amphiphilic comb macromolecules with different distribution statistics of side-chain grafting sites: Mathematical modeling

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Abstract

The influence of the distribution statistics of side-chain grafting sites on the conformational properties of amphiphilic comblike macromolecules immersed in a solvent that is poor for the main chain and good for the side chains was studied. It was shown that the coil-globule transition for macromolecules with the protein-like distribution of side-chain grafting sites occurs at higher temperatures, wherein the size of the proteinlike macromolecules is generally smaller than that of the corresponding regular macromolecules. Regardless of distribution statistics of side-chain grafting sites, the coil-globule transition of comb macromolecules passes through the step of the formation of the beads-on-a-string conformation composed of micelle-like beads. The temperature dependence curves of the heat capacity exhibit at least two maximums associated with the coil-globule transition per se and the coalescence of the beads into a single globule. The coil-globule transition temperature is slightly dependent upon the degree of polymerization of the main chain and drops with a decrease in the degree of polymerization of the side chains. It was found that comb macromolecules can form spherical, disklike, or cylindrical globules, depending on the structural parameters.

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Authors and Affiliations

  1. Faculty of Physics, Moscow State University, Moscow, 119991, Russia

    A. A. Starostina & A. R. Khokhlov

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

    A. A. Klochkov & V. V. Vasilevskaya

Authors
  1. A. A. Starostina
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  2. A. A. Klochkov
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  3. V. V. Vasilevskaya
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  4. A. R. Khokhlov
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Corresponding author

Correspondence to V. V. Vasilevskaya.

Additional information

Original Russian Text © A.A. Starostina, A.A. Klochkov, V.V. Vasilevskaya, A.R. Khokhlov, 2008, published in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 9, pp. 1691–1703.

This work was supported by the Russian Foundation for Basic Research, project no. 05-03-33077; the Netherlands Organization for Scientific Research (NWO), project no. 047.011.2005.011; and the Russian Academy of Sciences Division of Chemistry and Materials Science under the basic research program “Design and Study of Next-Generation Macromolecules and Macromolecular Structures,” project “Investigation of Amphiphilic Macromolecules Exemplified By Structurally Complex Comb Polycations.”

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Starostina, A.A., Klochkov, A.A., Vasilevskaya, V.V. et al. Amphiphilic comb macromolecules with different distribution statistics of side-chain grafting sites: Mathematical modeling. Polym. Sci. Ser. A 50, 1008–1017 (2008). https://doi.org/10.1134/S0965545X08090101

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  • DOI: https://doi.org/10.1134/S0965545X08090101

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