Spiral Patterning of Au Nanoparticles on Au Nanorod Surface to Form Chiral AuNR@AuNP Helical Superstructures Templated by DNA Origami

Abstract

Plasmonic motifs with precise surface recognition sites are crucial for assembling defined nanostructures with novel functionalities and properties. In this work, a unique and effective strategy is successfully developed to pattern DNA recognition sites in a helical arrangement around a gold nanorod (AuNR), and a new set of heterogeneous AuNR@AuNP plasmonic helices is fabricated by attaching complementary-DNA-modified gold nanoparticles (AuNPs) to the predesigned sites on the AuNR surface. AuNR is first assembled to one side of a bifacial rectangular DNA origami, where eight groups of capture strands are selectively patterned on the other side. The subsequently added link strands make the rectangular DNA origami roll up around the AuNR into a tubular shape, therefore giving birth to a chiral patterning of DNA recognition sites on the surface of AuNR. Following the hybridization with the AuNPs capped with the complementary strands to the capture strands on the DNA origami, left-handed and right-handed AuNR@AuNP helical superstructures are precisely formed by tuning the pattern of the recognition sites on the AuNR surface. Our strategy of nanoparticle surface patterning innovatively realizes hierarchical self-assembly of plasmonic superstructures with tunable chiroptical responses, and will certainly broaden the horizon of bottom-up construction of other functional nanoarchitectures with growing complexity.

Biomolecule‐Enabled Chiral Assembly of Plasmonic Nanostructures

“…In another recent approach employing bifacial origami, Shen et al. further developed heterogeneous Au NR@Au NP helices by winding the origami around the Au NR and attaching eight Au NPs on the same origami …”

“…In another recent approach employing bifacial origami,S hen et al furtherd eveloped heterogeneousA uN R@Au NP helices by winding the origami around the Au NR and attaching eight Au NPs on the same origami. [34] DNA helix bundles can be used as another template to create well-defined helical plasmonic structures. Liedl and coworkers utilized 24-helix bundles designed to provide 9h elical decoration sites (Figure 5d).…”

Valency Control and Functional Synergy in DNA‐Bonded Nanomolecules

“…Based on an AuNR inserted in the closed DNA origami clamp as discussed before, Wang et al. have recently realized a spiral arrangement of AuNPs around the AuNR (Figure G) . This work benefits from the highly addressable DNA origami sheath clamping the AuNR, which can be decorated with DNA linkers to assemble the AuNPs into a helical structure.…”

DNA‐Mediated Assembly of Gold Nanoparticles and Applications in Bioanalysis

“…Other techniques, such as anisotropic functionalization of DNA onto nanoparticles, controlled triplex formation, DNA nanocage, DNA origami as templates for the self‐assembly of nanoparticles or polymerase chain reaction (PCR) on the nanoparticle surfaces, are feasible options to generate substantial 0D assembled structures.…”

“…Adjusting the ratio of DNA to the AuNPs might generate single-DNA-functionalized large-sized AuNPs. [41,42] Other techniques, such as anisotropic functionalizationo f DNA onto nanoparticles, [39,[43][44][45] controlled triplex formation, [46] DNA nanocage, [47,48] DNA origami as templates for the self-assembly of nanoparticles [49][50][51] or polymerase chain reaction (PCR) on the nanoparticle surfaces, [52] are feasible options to generate substantial 0D assembled structures.…”