Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

Abstract

Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB controls the patch morphology to spherical, cylindrical, bicontinuous and lamellar. The independent control over both parameters allows constructing combinatorial libraries of unprecedented solution nanostructures, including spheres-on-cylinders/sheets/vesicles, cylinders-on-sheets/vesicles, and sheets/vesicles with bicontinuous or lamellar membrane morphology (patchy polymersomes). The derived parameters provide a logical toolbox towards complex self-assemblies for soft matter nanotechnologies.

Facile assembly and loading of theranostic polymersomes via multi-impingement flash nanoprecipitation

“…FNP may therefore present a rapid and scalable alternative method of formation of polymeric biocontinuous nanostructures in simple aqueous solutions without the need for additives or complex block copolymer architectures (e.g. dendritic-linear [32], multiblock [55] and miktoarm stars [56]). Switching the solvent to dimethylformamide (δ = 24.8 MPa 1/2 ) resulted in the formation of micelles from copolymer 4†, which was initially found to assemble vesicles when THF was instead used as the common solvent (Fig.…”

Self‐Assembly of Multiblock Copolymers

“…In a recent work on MCMs assembled from PS‐ b ‐PB‐ b ‐P t BMA triblock terpolymers, the P t BMA corona was systematically shortened while keeping the PS/PB core volumes constant. The resulting combinatorial table of observed MCMs and morphologies is given in Figure . With decreasing corona, the micelle shape first changed from spherical to cylindrical, and then to bilayer sheets and vesicles.…”

Block Copolymer Micelles with Inverted Morphologies

“…[2] Very recently, "classical" BCP micelles were further diversified into subclasses by adding internal core morphology or by compartmentalizing the corona. [3] In the wider context, substantial progress has been achieved with crystallization-driven living growth and polymerization-induced self-assembly,a nd by programming lifetimes to give transient BCP self-assemblies. [4][5][6] Irrespective of the complexity,t he overall shape of classical BCP solution morphologies has long been parameterized with the packing parameter p,w hich in first approximation is am easure for chain packing, balancing the volume demand of the core versus that of the corona.…”