Self-assembly concepts for multicompartment nanostructures

Abstract

Compartmentalization is ubiquitous to many biological and artificial systems, be it for the separate storage of incompatible matter or to isolate transport processes. Advancements in the synthesis of sequential block copolymers offer a variety of tools to replicate natural design principles with tailor-made soft matter for the precise spatial separation of functionalities on multiple length scales. Here, we review recent trends in the self-assembly of amphiphilic block copolymers to multicompartment nanostructures (MCNs) under (semi-)dilute conditions, with special emphasis on ABC triblock terpolymers. The intrinsic immiscibility of connected blocks induces short-range repulsion into discrete nano-domains stabilized by a third, soluble block or molecular additive. Polymer blocks can be synthesized from an arsenal of functional monomers directing self-assembly through packing frustration or response to various fields. The mobility in solution further allows the manipulation of self-assembly processes into specific directions by clever choice of environmental conditions. This review focuses on practical concepts that direct self-assembly into predictable nanostructures, while narrowing particle dispersity with respect to size, shape and internal morphology. The growing understanding of underlying self-assembly mechanisms expands the number of experimental concepts providing the means to target and manipulate progressively complex superstructures.

Controllable multicompartment morphologies from cooperative self-assembly of copolymer–copolymer blends

“…In an A 11 selective solution, the cooperative self-assembly of the AB/AC blends depends largely on factors such as relative segregation degree of AB and AC, compatibility of B and C and relative concentration of AB and AC 14,50 . Figure 3 Multicompartment micelles with separated AB shell and AC core (a AB = 60, a AC = 37.04, a BC = 45) should be dependent on the relative concentration of the two copolymers.…”

“…To further expand the number of morphologies, blending of ternary AB/AC/AD diblock copolymers leads to multicompartment micelles with more complex compartment distributions in the core or shell 18,50 . Based on the assembly pathways in the binary system above, the central challenge of the ternary system lies in confining multiple phases that spontaneously blend or separate under different incompatibilities, which is driven by unfavorable mixing enthalpy 14 .…”

“…However, due to the complexity of coexisting mixed micelles from architecturally and chemically versatile block copolymers 14,18,50,51 , many more explorations are needed.…”

“…To date, most studies involving the co-assembly of block copolymer blends have focused on the synthesis of polymers with particular chain architecture and electrostatic interaction 18,50 , which, as indicated in the cone-column mechanism, provide a specific driving force for phase separation. These two aspects are mainly related to the intra-(relating to chain stretching) and inter-(relating to block incompatibility) repulsions of block copolymers.…”

Self-assembly of diphenylalanine with preclick components as capping groups

“…[1][2][3][4][5] As these interactions are ubiquitous in biological systems, nature has inspired artificial building blocks amenable to self-assemble into supramolecular structures. [6][7][8][9] With respect to biological building blocks, peptides are of great interest for materials science due to their structural simplicity, functional versatility, cost effectiveness, and widespread applications.…”