Polymer vesicles as robust scaffolds for the directed assembly of highly crystalline nanocrystals

We report the incorporation of various inorganic nanoparticles (NPs) (PbS, LaOF, LaF(3), and TiO(2), each capped by oleic acid, and CdSe/ZnS core/shell QDs capped by trioctylphosphine oxide) into vesicles (d = 70-150 nm) formed by a sample of poly(styrene-b-acrylic acid) (PS(404)-b-PAA(62), where the subscripts refer to the degree of polymerization) in mixtures of tetrahydrofuran (THF), dioxane, and water. The block copolymer formed mixtures of crew-cut micelles and vesicles with some enhancement of the vesicle population when the NPs were present. The vesicle fraction could be isolated by selective sedimentation via centrifugation, followed by redispersion in water. The NPs appeared to be incorporated into the PAA layers on the internal and external walls of the vesicles (strongly favoring the former). NPs on the exterior surface of the vesicles could be removed completely by treating the samples with a solution of ethylenediaminetetraacetate (EDTA) in water. The triangular nanoplatelets of LaF(3) behaved differently. Stacks of these platelets were incorporated into solid colloidal entities, similar in size to the empty vesicles that accompanied them, during the coassembly as water was added to the polymer/LaF(3)/THF/dioxane mixture.