Active Self‐Assembly of Train‐Shaped DNA Nanostructures via Catalytic Hairpin Assembly Reactions

Biomolecular self-assembly is a powerful approach for fabricating supramolecular architectures. Over the past decade, a myriad of biomolecular assemblies, such as self-assembly proteins, lipids, and DNA nanostructures, have been used in a wide range of applications, from nano-optics to nanoelectronics and drug delivery. The method of controlling when and where the self-assembly starts is essential for assembly dynamics and functionalization. Here, train-shaped DNA nanostructures are actively self-assembled using DNA tiles as artificial "carriages," hairpin structures as "couplers," and initiators of catalytic hairpin assembly (CHA) reactions as "wrenches." The initiator wrench can selectively open the hairpin couplers to couple the DNA tile carriages with high product yield. As such, DNA nanotrains are actively prepared with two, three, four, or more carriages. Furthermore, by flexibly modifying the carriages with "biotin seats" (biotin-modified DNA tiles), streptavidin "passengers" are precisely arranged in corresponding seats. The applications of the CHA-triggered self-assembly mechanism are also extended for assembling the large DNA origami dimer. With the creation of 1D architectures established, it is thought that this CHA-triggered self-assembly mechanism may provide a new element of control for complex autonomous assemblies from a variety of starting materials with specific sites and times.