The regulated self-assembly behaviors of block polyelectrolyte solutions under electric fields.

Block polyelectrolyte (PE) self-assembly has critical applications in biomedicine and energy materials, but achieving controllable assembly remains challenging. Using molecular dynamics simulations, we investigate how external electric fields regulate block PE self-assembly in solution. Varying the field strength and dimension enables continuous, controllable transitions among multimeric, network, planar, columnar, wormlike, and sawtooth chain structures. Mechanistically, increasing field strength drives monomers and counterions in opposite directions, enhancing electrostatic repulsion and destabilizing the micellar hydrophobic core. Core dissociation triggers structural reconstruction and phase transitions. Increasing the electric field dimension amplifies both intensity and spatial anisotropy, regulating micelle alignment. The results demonstrate that the application of an electric field can effectively tune block PE self-assembly toward functional solution-based materials.