Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of complex materials. For block copolymers, the last decade witnessed great progress in diversifying the structural complexity of solution-based assemblies into multicompartment micelles. However, a general understanding of what governs multicompartment micelle morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. Here we demonstrate how to create homogeneous multicompartment micelles with unprecedented structural control via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined multicompartment micelles with precisely tunable patchiness, while using simple linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of multicompartment micelles into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects.

Recent advances in polymer synthesis have significantly enhanced the ability to rationally design block copolymers with tailored functionality. The self-assembly of these macromolecules in the solid state or in solution allows the formation of nanostructured materials with a variety of properties and potential functions. This Review illustrates recent progress in the field of block copolymer materials by highlighting selected emerging applications.

The concept of hierarchical bottom-up structuring commonly encountered in natural materials provides inspiration for the design of complex artificial materials with advanced functionalities. Natural processes have achieved the orchestration of multicomponent systems across many length scales with very high precision, but man-made self-assemblies still face obstacles in realizing well-defined hierarchical structures. In particle-based self-assembly, the challenge is to program symmetries and periodicities of superstructures by providing monodisperse building blocks with suitable shape anisotropy or anisotropic interaction patterns ('patches'). Irregularities in particle architecture are intolerable because they generate defects that amplify throughout the hierarchical levels. For patchy microscopic hard colloids, this challenge has been approached by using top-down methods (such as metal shading or microcontact printing), enabling molecule-like directionality during aggregation. However, both top-down procedures and particulate systems based on molecular assembly struggle to fabricate patchy particles controllably in the desired size regime (10-100 nm). Here we introduce the co-assembly of dynamic patchy nanoparticles--that is, soft patchy nanoparticles that are intrinsically self-assembled and monodisperse--as a modular approach for producing well-ordered binary and ternary supracolloidal hierarchical assemblies. We bridge up to three hierarchical levels by guiding triblock terpolymers (length scale ∼10 nm) to form soft patchy nanoparticles (20-50 nm) of different symmetries that, in combination, co-assemble into substructured, compartmentalized materials (>10 μm) with predictable and tunable nanoscale periodicities. We establish how molecular control over polymer composition programs the building block symmetries and regulates particle positioning, offering a route to well-ordered mixed mesostructures of high complexity.

Interpolyelectrolyte complexes (IPECs) are typically formed when two polyelectrolytes of opposite charge are mixed together in solution. We present an overview of different strategies for the preparation of micellar IPECs, i.e., structures where such IPEC domains form the core or the shell of micelles. In addition, vesicular architectures are considered, where the IPEC domain forms a membrane layer. One intriguing feature of IPECs is that their formation can be directed, their stability towards changes in pH or ionic strength can (to a certain extent) be predicted, and their size can be controlled. Especially the use of ionic/non-ionic block copolymers offers unique potential for the preparation of well-defined and sophisticated nanostructured materials. We also discuss possible applications, especially in the field of life sciences, including biocompatibility, the controlled uptake/release of guest substances, the immobilization of enzymes, or the controlled formation of inorganic/organic hybrid materials.

Nacre-mimetics hold great promise as mechanical high-performance and functional materials. Here we demonstrate large progress of mechanical and functional properties of self-assembled polymer/nanoclay nacre-mimetics by using synthetic nanoclays with aspect ratios covering three orders in magnitude (25-3,500). We establish comprehensive relationships among structure formation, nanostructuration, deformation mechanisms and mechanical properties as a function of nanoclay aspect ratio, and by tuning the viscoelastic properties of the soft phase via hydration. Highly ordered, large-scale nacre-mimetics are obtained even for low aspect ratio nanoplatelets and show pronounced inelastic deformation with very high toughness, while those formed by ultralarge nanoplatelets exhibit superb stiffness and strength, previously only reachable for highly crosslinked materials. Regarding functionalities, we report formerly impossible glass-like transparency, and excellent gas barrier considerably exceeding earlier nacre-mimetics based on natural nanoclay. Our study enables rational design of future high-performance nacre-mimetic materials and opens avenues for ecofriendly, transparent, self-standing and strong advanced barrier materials.