We describe the synthesis and self-assembly of amphiphilic semiconducting polymers composed of a polythiophene derivative (i.e., poly [3-(2,5,8,11-tetraoxatridecanyl)thiophene] (PTOTT)) and an oligonucleotide, DNA-b-PTOTT. These new bioconjugated polymers combine the excellent optoelectronic properties of semiconducting polymers and the programmable molecular recognition properties of DNA. Because of the unique combination of rigid polythiophene and highly negatively charged DNA, they self-assemble into size-controllable vesicles in water. DNA-modified one-dimensional polythiophene nanoribbons were formed by simultaneous assembly of DNA-b-PTOTT with PEG-b-PTOTT, demonstrating that various types of DNA-modified functional nanostructures can be formed by the mixed assembly. This approach offers a new pathway to couple various types of soft optoelectronic nanostructures with DNA's molecular recognition properties.

The emulsion‐based self‐assembly of nanoparticles into low‐dimensional superparticles of hollow vesicle‐like assemblies is reported. Evaporation of the oil phase at relatively low temperatures from nanoparticle‐containing oil‐in‐water emulsion droplets leads to the formation of stable and uniform sub‐micrometer vesicle‐like assembly structures in water. This result is in contrast with those from many previously reported emulsion‐based self‐assembly methods, which produce solid spherical assemblies. It is found that extra surfactants in both the oil and water phases play a key role in stabilizing nanoscale emulsion droplets and capturing hollow assembly structures. Systematic investigation into what controls the morphology in emulsion self‐assembly is carried out, and the approach is extended to fabricate more complex rattle‐like structures and 2D plates. These results demonstrate that the emulsion‐based assembly is not limited to typical thermodynamic spherical assembly structures and can be used to fabricate various types of interesting low‐dimensional assembly structures.

The self‐assembly of DNA block‐copolymers and nanoparticles yields hybrid nanostructures with useful properties of incorporated nanoparticles and a high density DNA layer on the exterior. Remarkably, they exhibit drastically enhanced binding capability to complementary DNA even at very low salt concentrations where isolated DNA strands do not form duplex structure. This extraordinary binding capability along with the high selectivity allows for efficient duplex DNA detection.

DNA-conjugated metal nanoparticles have attracted enormous attention for biological and medical applications, owing to their unusual DNA melting characteristics as well as unique optical and catalytic properties. The combination of these unique properties has not only led to the development of DNA-detection technologies with remarkably high selectivity and sensitivity, but also to the development of gene therapeutic agents with high efficacy and efficiency. In this review, we present a comprehensive coverage on their applications in detecting, manipulating, and delivering genes.

Here, we report DNA-induced polymer segregation and DNA island formation in binary block copolymer assemblies. A DNA diblock copolymer of polymethylacrylate-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 co-assembled 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 has 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.