Influence of Dipole Orientation on Solution Properties of Polyzwitterions

We have studied the influence of segmental dipole orientation on the solution properties of polyzwitterions using dynamic and static light scattering of poly­(2-methacryloyloxyethyl phosphorylcholine) (PMPC), n-butyl-substituted choline phosphate polymers (PMBP), and their diblock (PMPC-b-PMBP) copolymers in solutions of different salt concentration. We find that these three structures exhibit dramatically different aggregation behaviors. For the conditions in our study, PMPC is a swollen excluded-volume chain without significant presence of dipolar correlations as evident from the lack of sensitivity to the ionic strength of the solution. In contrast, PMBP self-assembles into finite-sized structures in solution, which are stabilized by electrostatic dipole–dipole interactions. Evidence of these interactions is also present in the diblock polymer, PMPB-b-PMPC, which self-assembles into two distinct, stable aggregates in addition to unaggregated chains. These results contribute to the breadth of understanding of polyzwitterions in solution and provide a platform for future simulation and experimental explorations.