Morphology Control of Multicompartment Micelles in Water through Hierarchical Self-Assembly of Amphiphilic Terpolymers

Abstract

Multicompartment micelles (MCMs) allow the simultaneous storage of multiple cargoes such as dyes, catalysts, or drugs, and have therefore gained attention in catalysis, nanotechnology, and nanomedicine. In the present work, we describe design rules to control the morphology of MCMs in water including spheres, cylinders, sheets, and vesicles. For that, we synthesized a series of poly(ethylene oxide) (PEO)-b-polystyrene (PS)-b-poly(methyl acrylate) (PMA) triblock terpolymers and systematically varied the length of the PS and PMA block. Using a stepwise hierarchical assembly process, we first form patchy precursor micelles in organic solvent with PS core and mixed PEO/PMA corona. In the second step, these micelles act as subunits, which assemble (or cluster) in water into MCMs, where PEO forms the stabilizing corona, PS the compartment, and PMA the inner core. We find that the shape of the final MCM can be predicted by ascribing a Janus balance to precursor micelles as the molar ratio of PEO to PMA, which provides a synthetic handle to target specific MCM morphologies.

Controlling self-assembling co-polymer coatings of hydrophilic polysaccharide substrates via co-polymer block length ratio

“…In agreement with our findings, effects include e.g. transitioning from ordered to disordered segregation [86], multicore assembly control [87][88][89][90], and length dependent segregation of the block components according to local curvature [91,92]. For more complex architectures, such as H-shaped polymers, an even richer microphase segregation phase landscape arises [93].…”

Confinement Assembly of Terpolymer‐Based Janus Nanoparticles

“…The JB ranges from 0 to 100 (isotropic spheres) and is defined here as the molar fraction of the PS and PMMA units in the corona, i.e., JB PS = DP n,PS /(DP n,PS + DP n,PMMA ) × 100 (JB PMMA = 100 − JB PS ). [61,62] The JB and other polymer specific parameters are listed in Table S2 (Supporting Information).…”

Regulation of the nanostructures self-assembled from an amphiphilic azobenzene homopolymer: influence of initial concentration and solvent solubility parameter

“…have been widely used to control the shape, size, and microstructure of the assemblies. In addition, post self-assembly methods such as stimuli-responsive shape transformation, 27,28 hierarchical self-assembly, 29,30 and particle fusion 31–33 also allow the controlling over the microstructure of soft nanomaterials.…”