DNA Island Formation on Binary Block Copolymer Vesicles.

Here, we report DNA-induced polymer segregation and DNA island formation in binary block copolymer assemblies. A DNA diblock copolymer of polymethyl acrylate-block-DNA (PMA-b-DNA) and a triblock copolymer of poly(butadiene)-block-poly(ethylene oxide)-block-DNA (PBD-b-PEO-b-DNA) were synthesized, and each was coassembled with a prototypical amphiphilic polymer of poly(butadiene)-block-poly(ethylene oxide) (PBD-b-PEO). The binary self-assembly of PMA-b-DNA and PBD-b-PEO resulted in giant polymersomes with DNA uniformly distributed in the hydrophilic PEO shell. When giant polymersomes were connected through specific DNA interactions, DNA block copolymers migrated to the junction area, forming DNA islands within polymersomes. These results indicate that DNA hybridization can induce effective lateral polymer segregation in mixed polymer assemblies. The polymer segregation and local DNA enrichment have important implications in DNA melting properties, as mixed block copolymer assemblies with low DNA block copolymer contents can still exhibit useful DNA melting properties that are characteristic of DNA nanostructures with high DNA density.