From sea-urchins to starfishes: controlling the adsorption of star-branched polyelectrolytes on charged walls

Abstract

We demonstrate that star-branched polyelectrolytes are a versatile soft component forming a variety of well-characterised conformations upon electrostatic complexation on oppositely charged planar surfaces. We discover and characterise five complexation shapes, described by a two-dimensional morphological order parameter. These shapes are distinguished on the basis of their deviations from sphericity, the orientation of the polyelectrolyte arms, and the equilibrium centre-to-surface distance of the stars. Conformational transformations can be steered by changing the electrostatic surface–star coupling and/or the star functionality. For low functionalities and/or strong external fields, full collapse of the star onto the wall, forming a starfish configuration, is observed. Otherwise, partially adsorbed states with a fraction of chains pointing away from the surface and with the star core being detached from the wall are formed.