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Self-assembly of an amphiphilic diblock copolymer in aqueous solutions: Effect of linear charge density of an ionogenic block

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Abstract

The effect of linear charge density of the ionogenic block on the self-assembly of the amphiphilic diblock copolymer based on polystyrene and poly(4-vinylpyridine) partially alkylated by ethyl bromide in aqueous solutions at pH 9 is studied by UV spectrophotometry and dynamic and static light scattering. During dispersion in water, the diblock copolymer forms micelles composed of the hydrophobic polystyrene core and the amphiphilic lyophilizing corona consisting of N-ethyl-4-vinylpyridinium bromide ionic units and uncharged units of 4-vinylpyridine. It is shown that with a change in the fraction of charged units in the lyophilizing block from 30 to 90 mol %, the thermodynamic quality of the solvent with respect to micelles is slightly monotonically improved and the hydrodynamic sizes of micelles in 0.05 M NaCl are increased. At the same time, such properties as the weight-average degree of aggregation of macromolecules in a micelle, the dimensions of the corona in 0.05 M NaCl, and the dispersion stability of micelles in aqueous-saline solution abruptly change when the content of charged units in the lyophilizing block is 60–70 mol %. After addition of oppositely charged polyelectrolytes or low-molecular-mass surfactants into the micellar solution, polyelectrolyte complexes form and the solubility of these complexes in an excess oppositely charged component likewise changes abruptly with variation in the fraction of charged units in the range from 60 to 70 mol %. A qualitative description is advanced to explain the effect of linear charged density of the lyophilizing block on the self-assembly and complexing behavior of diblock copolymers in aqueous solutions.

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Authors and Affiliations

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

    A. I. Kulebyakina, E. A. Lysenko, P. S. Chelushkin, A. V. Kabanov & A. B. Zezin

  2. Department of Pharmaceutical Sciences, University of Nebraska Medical Center, Omaha, NE, 68198, USA

    A. V. Kabanov

Authors
  1. A. I. Kulebyakina
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  2. E. A. Lysenko
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  3. P. S. Chelushkin
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  4. A. V. Kabanov
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  5. A. B. Zezin
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Correspondence to E. A. Lysenko.

Additional information

Original Russian Text © A.I. Kulebyakina, E.A. Lysenko, P.S. Chelushkin, A.V. Kabanov, A.B. Zezin, 2010, published in Vysokomolekulyarnye Soedineniya, Ser. A, 2010, Vol. 52, No. 6, pp. 908–920.

This work was supported by the Russian Foundation for Basic Research (project no. 06-03-90153-NNF_a) and the Ministry of Education and Science of the Russian Federation (State Contract 02.740.11.0266).

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Kulebyakina, A.I., Lysenko, E.A., Chelushkin, P.S. et al. Self-assembly of an amphiphilic diblock copolymer in aqueous solutions: Effect of linear charge density of an ionogenic block. Polym. Sci. Ser. A 52, 574–585 (2010). https://doi.org/10.1134/S0965545X10060027

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  • DOI: https://doi.org/10.1134/S0965545X10060027

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