title: Charge-controlled nano-structuring in partially collapsed star-shaped macromolecules.
abstract: Hydrophobic polyelectrolytes exhibit intra-molecular nano-scale self-organization instead of macroscopic phase separation because of the interplay between short-range hydrophobic attraction and long-range electrostatic repulsion. We aim to unravel how the morphology of the intra-molecular nanostructures can be controlled through the topology of the macromolecule on one hand and by adjustable ionization on the other hand. Specifically, we focus on hydrophobic star-branched polyelectrolytes, composed of either strong or weak acidic monomers. While both collapse in a globule when uncharged, and expand to full stretching of arms at high ionization, they exhibit quite different intermediate scenarios. For the strong ones, we observe the formation of bundles of arms as the main structural motif, and for the weak ones the intramolecular micelle-like structure is found at the same overall charge of the macromolecule. Here intramolecular disproportionation leaves some arms in a collapsed virtually neutral core, while others are substantially ionized and stretched in the corona.
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 8, 128 00 Praha 2, Czech Republic.
authors.forename: Filip
authors.initials: F
authors.lastname: Uhlík
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 8, 128 00 Praha 2, Czech Republic.
authors.forename: Peter
authors.initials: P
authors.lastname: Košovan
authors.affiliation: Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004 St. Petersburg, Russia and St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101, St. Petersburg, Russia.
authors.forename: Ekaterina B
authors.initials: EB
authors.lastname: Zhulina
authors.affiliation: St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101, St. Petersburg, Russia and CNRS, UMR 5254 - IPREM - Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Maériaux, 2 avenue du Président Angot, 64053 Pau, France. oleg.borisov@univ-pau.fr.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Borisov