Theoretical study of branched polyelectrolytes

ii CHARLES UNIVERSITY Faculty of Science Department of Physical and Macromolecular Chemistry Doctoral Thesis Theoretical Study of Branched Polyelectrolytes by Varvara PROKACHEVA Abstract This thesis is dedicated to the theoretical study of branched pH-responsive polyelec- trolytes including stars, molecular brushes as well as hydrogels in dilute aqueous salt solutions. It was investigated how external parameters, such as ionic strength, pH, and solvent quality affect the properties and the internal structure of those poly- electrolytes. The study was carried out by the development of an analytical theory which results were validated by the numerical Scheutjens-Fleer self-consistent field method as well as Monte Carlo and molecular dynamics simulations. A competition between electrostatic repulsions with short-range solvophobic in- teractions leads to complex patterns within intramolecular self-organization of bran- ched polyelectrolytes. That results in the formation of domain structures, in partic- ular, core-shell and pearl necklace structures in stars and molecular brushes, respec- tively. These domains are formed by almost neutral collapsed chains and stabilized by stretched and ionized chains. This study is relevant both in terms of creating new functional polymer materials for a wide range of..