Self-Assembly of Block Copolymer Nanostructures

Block copolymers, comprising covalently linked segments with distinct solubility or crystallinity, can spontaneously organise into nanostructures whose shapes and sizes are dictated by a balance of enthalpic and entropic forces. Control over this self‐assembly process has been greatly enhanced by the advent of crystallisation-driven self‐assembly (CDSA), in which one block crystallises under mild conditions to nucleate and direct the formation of micelles, platelets or fibres with narrow dispersity. A seeded or “living” variant of CDSA further permits precise tuning of length and morphology through the addition of unimeric polymer to preformed crystalline seeds. Beyond purely polymeric assemblies, co‐crystallisation and stereocomplexation between complementary blocks can yield hybrid or stereocomplex micelles with bespoke symmetries and enhanced stability. These advances have unlocked hierarchical and spatially resolved functionalities, from segmented cores for programmed release to anisotropic nanosheets for electronic or adhesive applications. Such materials find use in drug and gene delivery, nanocomposite hydrogels, optical data storage, catalysis and surface patterning, highlighting the global significance of programmable block‐copolymer architectures.

Research from Nature Portfolio

Recent studies have exploited co‐crystallisation to induce unconventional symmetry in hybrid nanocrystals. One report demonstrates how the controlled inhibition of polymer crystallisation promotes oriented attachment of twinned domains, yielding triangular nanoplates with symmetry higher than that of the underlying lattice. Another investigation has extended living CDSA to generate uniform 2D platelet micelles with compositionally segmented cores. By blending different crystallisable homopolymers in a seeded growth protocol, researchers achieved spatially defined chemical domains whose selective hydrolytic degradation illustrates new routes to stimuli‐responsive delivery vehicles. These studies underscore the power of combining kinetic control and co‐crystallisation to engineer nanostructures with precise shapes, internal architectures and functional contrasts.

Self-Assembly of Block Copolymer Nanostructures publication trend

The graph below shows the total number of articles in self-assembly of block copolymer nanostructures across all publications each year (not limited to Nature Index journals).

Technical terms

Amphiphilic block copolymer: Polymer containing covalently linked segments with differing affinities for solvent, driving phase separation and self‐assembly.

Crystallisation-driven self-assembly (CDSA): Process in which a crystallisable block nucleates and grows under kinetic control to form well‐defined micelles or platelets.

Living CDSA: Seeded-growth variant of CDSA where unimer addition to crystalline seeds enables precise control of nanostructure length and dispersity.

Stereocomplexation: Co‐crystallisation between enantiomeric polymer blocks, producing hybrid morphologies and enhanced thermal or mechanical stability.

Corona: The solvated, amorphous block of a micelle that surrounds and stabilises the crystalline core in solution.

References

1. 2D Hierarchical Microbarcodes with Expanded Storage Capacity for Optical Multiplex and Information Encryption. Advanced Materials (2023).
2. Apparent symmetry rising induced by crystallization inhibition in ternary co-crystallization-driven self-assembly. Nature Communications (2023).
3. Uniform segmented platelet micelles with compositionally distinct and selectively degradable cores. Nature Chemistry (2023).
4. Tuning the Functionality of Self-Assembled 2D Platelets in the Third Dimension. Journal of the American Chemical Society (2023).
5. Emerging applications for living crystallization-driven self-assembly. Chemical Science (2021).