Design and characterization of self-assembled nanostructures of block copolymers in solution.

摘要

Self-assembling amphiphilic block copolymers have been studied extensively due to their ability to form a wide range of morphologies including spheres, cylinders, and vesicles. Changing the molecular composition of the block copolymer, the relative block lengths, and the solution conditions can alter the assembly behavior. The main goal of this dissertation is to investigate the self-assembly of two different amphiphilic block copolymer systems in an effort to controllably make different assembled structures.;Amphiphilic, triblock copolymers of poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene (PAA-PMA-PS) in tetrahydrofuran (THF)/water solvent mixtures were studied. The solution conditions and the relative block lengths were varied, and complexation with an amine counterion was used to influence the self-assembly of these materials. A variety of structures were observed including phase-separated nanoparticles, bulk-like lamellar phase separation, spherical, cylindrical, and disk-like micelles, as well as toroidal assemblies. The specific structure formed was dependent on the composition of the triblock copolymer, the amount and valency of the counterion present, and the THF to water volume ratio. The structure of polymer nanoparticles and networks formed in low water content systems was examined. The size of the nanoparticles and whether separated nanoparticles vs. an interconnected network was formed was controlled via solvent composition. Importantly, both the nanoparticles and network phases contained their own inherent nanostructure due to local phase separation of the block copolymers. This phase behavior within the nanoparticles could be tuned, i.e. porous or lamellar internal structure, by changing the valency of the amine counterion. Cryo-transmission electron microscopy (TEM), traditional TEM, and neutron scattering were used to examine these samples.;In addition to these triblock copolymers, amphiphilic diblock copolypeptides of hydrophobic leucine (L) and hydrophilic lysine (K) with poly(ethylene glycol) side groups were investigated. The effect of the copolypeptide design on the resulting morphology was studied by examining diblock compositions with different block lengths and secondary structures. It was determined that the secondary structure of these peptides plays a significant role in influencing the assembly of these materials.