Complex DNA Architectonics─Self-Assembly of Amphiphilic Oligonucleotides into Ribbons, Vesicles, and Asterosomes

Abstract

The precise arrangement of structural subunits is a key factor for the proper shape and function of natural and artificial supramolecular assemblies. In DNA nanotechnology, the geometrically well-defined double-stranded DNA scaffold serves as an element of spatial control for the precise arrangement of functional groups. Here, we describe the supramolecular assembly of chemically modified DNA hybrids into diverse types of architectures. An amphiphilic DNA duplex serves as the sole structural building element of the nanosized supramolecular structures. The morphology of the assemblies is governed by a single subunit of the building block. The chemical nature of this subunit, i.e., polyethylene glycols of different chain length or a carbohydrate moiety, exerts a dramatic influence on the architecture of the assemblies. Cryo-electron microscopy revealed the arrangement of the individual DNA duplexes within the different constructs. Thus, the morphology changes from vesicles to ribbons with increasing length of a linear polyethylene glycol. Astoundingly, attachment of a N-acetylgalactosamine carbohydrate to the DNA duplex moiety produces an unprecedented type of star-shaped architecture. The novel DNA architectures presented herein imply an extension of the current concept of DNA materials and shed new light on the fast-growing field of DNA nanotechnology.

Tunable Electronic Structure via DNA-Templated Heteroaggregates of Two Distinct Cyanine Dyes

“…Using DNA nanotechnology, oligonucleotides with specific sequences can be designed to self-assemble into a variety of low-dimensional structures such as multi-armed junctions, dendrimers, hairpins, and loops . Much larger DNA structures with sizes on the order of hundreds of nanometers have also been realized through DNA origami, and similarly large vesicles, ribbons, and star-shaped structures have been self-assembled using chemically modified, amphiphilic duplex DNA where the ends are hydrophobic and the interior is hydrophilic. , In addition to having enormous structural diversity, DNA is amenable to a vast number of chemical modifications including dye labeling. By chemically attaching dyes to the DNA backbone, it is possible to bring dyes into close proximity at sub-nanometer separations.…”

Supramolecular assembly of pyrene–DNA conjugates: influence of pyrene substitution pattern and implications for artificial LHCs

“…containing hydrophobic (sticky) ends, has been shown to be a viable alternative for the formation of DNA-based nanostructures. [29][30][31][32][33][34][35] Recently, we reported the supramolecular self-assembly of 3′-end modified DNA conjugates into vesicles, using phenanthrene or tetraphenylethylene sticky ends. 36,37 The hydrophobic interactions between the aromatic overhangs are a key element for the self-assembly process.…”