(363b) Effect of Block Properties and Solvent Quality on Self-Assembly of Polyelectrolyte Block Copolymers

Polyelectrolyte block copolymers, which combine structural features of polyelectrolyte, block copolymers and surfactants, may self-assemble in a variety of nanoaggregates in aqueous environment, such as micelles, vesicles, lamellar mesophases or micellar aggregates. The morphology and size of formed aggregates are determined by the characteristically complex equilibrium of noncovalent forces (electrostatic, steric, hydrogen bonding, Van der Waals, and hydrophobic interactions). The strength of repulsive Coulomb interactions between the polyelectrolyte segments can be efficiently tuned by variations in ionic strength or/and pH in the aqueous solution. In order to explore the self-assembly process of polyelectrolyte block copolymers, we developed Dissipative Particle Dynamics (DPD) model of polyelectrolyte block copolymers with incorporated electrostatic interactions to achieve a good balance between reasonable physical description and computational feasibility. We applied this coarse-grained model to explore the influence of block length, block architecture, and solvent quality on the properties of the assemblies formed in aqueous solutions. Our DPD model enables us to obtain the main characteristics of the micelles formed (the aggregation number, the corona and core sizes, and anisotropy) as a function of the block length and salt concentration. Based on a comprehensive set of data obtained we constructed a morphological diagram of polyelectrolyte block copolymers in aqueous solution. The coarse-grained modeling and simulation, which is demonstrated as a complimentary approach in addition to experimental and theoretical methods, can deliver insight into self-assembly processes of block copolymers and provide evaluation of the size of aggregates obtained along with their scaling relation representation. The simulation results suggest that this coarse-grained simulation scheme gives a route wherein one can effectively and efficiently capture the self-assembly behaviors of polyelectrolyte block copolymers.