Research Article

Casting inorganic structures with DNA molds

See allHide authors and affiliations

Science  07 Nov 2014:
Vol. 346, Issue 6210, 1258361
DOI: 10.1126/science.1258361

You are currently viewing the abstract.

View Full Text

Structured Abstract

Introduction

The ability to manufacture inorganic nanoparticles (NPs) with arbitrarily prescribed three-dimensional (3D) shapes and positional surface modifications is essential to enabling diverse applications (e.g., in nano-optics and biosensing). However, it is challenging to achieve 3D arbitrary user-specified shapes with sub–5-nm resolution. Top-down lithography has limited resolution, particularly for 3D shapes; capping ligands can be used to tune the energy difference of selected crystallographic facets, but typically only for highly symmetric shapes with identical surface facets.

Embedded Image

Casting metal particles with prescribed 3D shapes using programmable DNA nanostructure molds. (Top) Schematic of computational shape-by-design framework to encode the user-specified 3D shape of an inorganic particle in the linear sequences of DNA. (Middle) Assembly of the mold and casting growth of the metal particle. (Bottom) Experimental characterization of cast products (transmission electron micrographs; scale bars, 20 nm).

Rationale

We developed a framework to program arbitrary 3D inorganic NPs using DNA, which serves both as an informational “genome” to encode the 3D shape of a NP and as a physical “fabricator” to retrieve the information and execute the instruction to manufacture the NP. Specifically, our method uses a computationally designed, mechanically stiff synthetic DNA nanostructure with a user-specified cavity as a “mold” to cast the target inorganic NP. The mold encloses a small gold (Au) “seed.” Under mild conditions, the Au seed grows into a larger metal NP that fills the entire cavity, thereby replicating its prescribed 3D shape. The remaining DNA mold additionally acts as a spatially programmable functionalization surface.

Results

Using this DNA nanocasting method, we constructed three distinct sub–25-nm 3D cuboid silver (Ag) NPs with three independently tunable dimensions. The shape versatility of DNA-based nanocasting was further demonstrated via the synthesis of Ag NPs with equilateral triangular, right triangular, and circular cross sections. The material versatility was demonstrated via synthesis of a Au cuboid in addition to the Ag NPs. The DNA mold served as an addressable coating for the casted NP and thus enabled the construction of higher-order composite structures, including a Y-shaped Ag NP composite and a quantum dot (QD)–Ag-QD sandwiched structure through one-step casting growth.

We investigated the key design parameters for stiff DNA molds through mechanical simulations. Multilayered DNA molds provided higher mechanical stiffness for confining NP growth within the mold than single-layer DNA molds, as confirmed by experimental observation.

We additionally characterized plasmonic properties of the designer equilateral Ag triangle and Ag sphere through electron energy loss spectroscopy. Tuning of particle symmetry produced a shape-specific spectrum, which is consistent with the predictions of electromagnetism-based simulations.

Conclusion

DNA nanocasting represents a new framework for the programmable digital fabrication of 3D inorganic nanostructures with prescribed shapes, dimensions, and surface modifications at sub– 5-nm resolution. The key design strategy is to encode linear sequences of DNA with the sophisticated user-specified 3D spatial and surface information of an inorganic NP, as well as to retrieve and execute the information to physically produce this structure via geometric confinement. Such a method may lead to computationally designed functional materials for the digital manufacture of optical nanocircuits, electronic nanocomputers, and perhaps even sophisticated inorganic nanorobots, each with their blueprints (or “genomes’’) encoded in the DNA molecules that constitute their “nanofabricators.”

Casting gold and silver with DNA origami

Controlling the size and shape of nanoparticles synthesized in solution can be challenging, especially if the goal is to create less symmetric shapes for use in electronic and plasmonic applications. Sun et al. show that DNA “origami”—nanostructures in which the contacts between DNA strands are designed to assemble a particular shape—are sufficiently stiff to act as a mold for the growth of gold and silver nanostructures. The authors created shapes, including a gold particle with a rectangular cross section and a silver triangle with designed plasmonic properties.

Science, this issue 10.1126/science.1258361

Abstract

We report a general strategy for designing and synthesizing inorganic nanostructures with arbitrarily prescribed three-dimensional shapes. Computationally designed DNA strands self-assemble into a stiff “nanomold” that contains a user-specified three-dimensional cavity and encloses a nucleating gold “seed.” Under mild conditions, this seed grows into a larger cast structure that fills and thus replicates the cavity. We synthesized a variety of nanoparticles with 3-nanometer resolution: three distinct silver cuboids with three independently tunable dimensions, silver and gold nanoparticles with diverse cross sections, and composite structures with homo- and heterogeneous components. The designer equilateral silver triangular and spherical nanoparticles exhibited plasmonic properties consistent with electromagnetism-based simulations. Our framework is generalizable to more complex geometries and diverse inorganic materials, offering a range of applications in biosensing, photonics, and nanoelectronics.

View Full Text