Valence-programmable nanoparticle architectures

Abstract

Nanoparticle-based clusters permit the harvesting of collective and emergent properties, with applications ranging from optics and sensing to information processing and catalysis. However, existing approaches to create such architectures are typically system-specific, which limits designability and fabrication. Our work addresses this challenge by demonstrating that cluster architectures can be rationally formed using components with programmable valence. We realize cluster assemblies by employing a three-dimensional (3D) DNA meshframe with high spatial symmetry as a site-programmable scaffold, which can be prescribed with desired valence modes and affinity types. Thus, this meshframe serves as a versatile platform for coordination of nanoparticles into desired cluster architectures. Using the same underlying frame, we show the realization of a variety of preprogrammed designed valence modes, which allows for assembling 3D clusters with complex architectures. The structures of assembled 3D clusters are verified by electron microcopy imaging, cryo-EM tomography and in-situ X-ray scattering methods. We also find a close agreement between structural and optical properties of designed chiral architectures.

Engineering Inorganic Materials with DNA Nanostructures

“… 60 − 63 Besides DNA-assisted NP crystals, DNA nanostructures have recently been harnessed as templates for the fabrication of versatile and arbitrary valence-programmable NP clusters thus opening up new avenues in customizing NP cluster geometry, composition, and application-specific properties. 64 …”

Rationally Programming Nanomaterials with DNA for Biomedical Applications

“…[88] In the recent studies, the group showed a new approach for creating designed clusters with symmetric and arbitrary arrangement of nanoparticles in space using reprogrammable 3D ball-like mesh DNA scaffold. [89] Recently, Chan and co-workers constructed a variety of novel Au-based hybrid nanoassemblies with the aid of DNA template. [90][91][92] Different from those in the single particle system, the biological delivery, and elimination properties could be tuned in the DNA assembled core-satellite (CS) superstructures (Figure 2a).…”

Designer Nanomaterials through Programmable Assembly

“…“Chromatic” (“colored”) binding represents the addition of specificity into a nano‐object's binding coordination and valence, and this chromatic bond can be encoded through one or multiple (“polychromatic”) strands [4g, 5g, 21a] . In this manner, it is largely different than isotropic particle systems coated with specific DNA sequences and presents another dimension in DNA‐framed particle systems.…”