Uniformly charged polyelectrolyte molecules disperse uniformly in aqueous electrolyte solutions, due to electrostatic repulsion between them. In stark contrast to this well-established result of homogeneous polyelectrolyte solutions, we report a phenomenon where an aqueous solution of positively charged poly(L-lysine) (PLL) exhibits precipitation of similarly charged macromolecules at low ionic strength and a homogeneous solution at very high ionic strength, with a stable mesomorphic state of spherical aggregates as an interlude between these two limits. The precipitation at lower ionic strengths that is orthogonal to the standard polyelectrolyte behavior and the emergence of the mesomorphic state are triggered by the presence of a monovalent small organic anion, acrylate, in the electrolyte solution. Using light scattering, we find that the hydrodynamic radius Rh of isolated PLL chains shrinks upon a decrease in electrolyte (NaBr) concentration, exhibiting the "anti-polyelectrolyte effect." In addition, Rh of the aggregates in the mesomorphic state depends on PLL concentration cp according to the scaling law, [Formula: see text]. Furthermore, at higher PLL concentration, the mesomorphic aggregates disassemble by a self-poisoning mechanism. We conjecture that all these findings can be attributed to both intra- and interchain dipolar interactions arising from the transformation of polycationic PLL into a physical polyzwitterionic PLL at higher concentrations of acrylate. The reported phenomenon of PLL exhibiting dipole-directed assembly of mesomorphic states and the anti-polyelectrolyte effect are of vital importance toward understanding more complex situations such as coacervation and formation of biomolecular condensates.
Keywords: aggregation; dipolar interaction; liquid–liquid phase separation; mesomorphism; polyelectrolytes.