Multicompartment and multigeometry nanoparticle assembly

Abstract

The directed or dynamic assembly of molecular components in solution is a simple and effective strategy to confine materials in desired geometries and length scales. We use a kinetic control strategy with block copolymer blending to construct complex nanoparticles through the demixing of unlike block copolymers within the same nanoscale particle. Successful nanoparticle construction relies on kinetic trapping of unlike block copolymers into the same nanoparticle with solution processing. Not only can we make nanoparticles with multiple internal compartments of a desired size, but we can also make nanoparticles of hybrid geometries (e.g. a blend of cylindrical and spherical geometries). These combination particles are kinetically trapped, non-equilibrium structures. However, the block copolymers are able to phase separate locally within the nanoscale particle, thus producing internal compartments and hybrid geometries.

Hierarchical Assembly of Complex Block Copolymer Nanoparticles into Multicompartment Superstructures through Tunable Interparticle Associations

“…Moreover, without being covalently linked in the same molecular backbone, components in the mixture are responsive to various external stimuli such as solvent exchange, [ 40 ] changes in temperature, pH, [ 41 ] ionic strength, [ 23 ] and assembly kinetics. [ 26 ] Also, the components are dynamic enough to demix internally into compartments of diverse sizes and geometries depending on the type and amount of block copolymers in the original mixture. Complex particles from block copolymer mixtures introduce opportunities for novel superstructures that are distinguished from rigid colloidal systems.…”

“…By taking advantage of synthetic methodologies to afford varied block copolymer structures, [11][12][13][14] and extensive exploration of molecular solution assembly, [ 5-10 , 15 ] block copolymer assemblies have exhibited prodigious morphological diversity at the nanoscale beyond traditional spheres, cylinders, and vesicles. Not only have particles been constructed with unique shapes, such as disks, [ 16 , 17 ] branched rods, [ 7 , 18 ] and toroids, [ 19 ] but new nanostructures with compositional complexity, or complex nanoparticles, such as anisotropic particles [ 20 , 21 ] that include patchy, [ 22 , 23 ] multicompartment, [ 14 , 24-26 ] and Janus particles, [ 26 ] also have been explored. Anisotropic particles created from block copoly mer assemblies contain a non-centrosymmetric distribution of both compositions and properties within the core and/or on the surface of the particles.…”

Nanoscale detection of metal-labeled copolymers in patchy polymersomes

“…10 We therefore also introduced DOTA labeling during the synthesis of a PMPC macromolecular chain trans fer agent (macro CTA) (Scheme 1, details in SI). MPC was polymerized in the presence of a small amount (targeting 1 per polymer chain, 1.38 achieved) of maleimidomonoamide DOTA to produce the desired In DOTA PMPC macro CTA ( ).…”

Disk-cylinder and disk-sphere nanoparticles via a block copolymer blend solution construction

“…Alternately, one can purposely mix different block copolymers with unlike block chemistries into multi-component nanoparticles with proper kinetic processing. The limited examples of this strategy have focused on block copolymer molecules with similar molecular weights and relative block fractions for the production of blended spheres 22,23 , cylinders that contain multiple block copolymers 15,[23][24][25] and blended vesicles 26,27 .…”