DNA-Encoded Protein Janus Nanoparticles

Abstract

Asymmetric functionality and directional interactions, which are characteristic of noncentrosymmetric particles, such as Janus particles, present an opportunity to encode particles with properties, but also a great synthetic challenge. Here, we exploit the chemical anisotropy of proteins, and the versatile chemistry of DNA to synthesize a protein-based Janus nanoparticle comprised of two proteins encoded with sequence-specific nucleic acid domains, tethered together by an interprotein "DNA bond". We use these novel nanoparticles to realize a new class of three-dimensional superlattice, only possible when two sides of the particle are modified with orthogonal oligonucleotide sequences. The low symmetry, intrinsic to Janus particles, enables the realization of unprecedented multicomponent nanoparticle superlattices with unique, hexagonal layered architectures. In addition, the interprotein "DNA bond" can be modulated to selectively expand the lattice in a single direction. The results presented herein not only emphasize the power of rationally designing nanoscale building blocks to create highly engineered colloidal crystals, but also establish a precedent for applications of multidomain DNA-encoded nanoparticles, especially in the field of colloidal crystallization.

Programmable Atom Equivalents: Atomic Crystallization as a Framework for Synthesizing Nanoparticle Superlattices

“…First, while early work in PAE synthesis revealed multiple routes to either patchy or asymmetrically functionalized particles, the particles synthesized with these methods have not yet been demonstrated to form ordered crystals, and breaking the symmetry of spherical building blocks remains a challenge. Nevertheless, by functionalizing specific sites on pseudo‐spherical proteins with DNA, PAEs were synthesized with tunable and precise bond distributions where both the number and direction of DNA linkages were controlled . Such constructs have been demonstrated to produce arrangements that are unachievable with isotropically functionalized spheres .…”

“…Nevertheless, by functionalizing specific sites on pseudo‐spherical proteins with DNA, PAEs were synthesized with tunable and precise bond distributions where both the number and direction of DNA linkages were controlled . Such constructs have been demonstrated to produce arrangements that are unachievable with isotropically functionalized spheres . It is even possible to functionalize different sites on the same protein with orthogonal DNA sticky ends, thereby yielding Janus‐type PAEs that assemble into 1D crystalline chains, or complex layered crystalline structures of PAEs that alternate in NP core identity (composition or size) (Section .).…”

“…Such constructs have been demonstrated to produce arrangements that are unachievable with isotropically functionalized spheres . It is even possible to functionalize different sites on the same protein with orthogonal DNA sticky ends, thereby yielding Janus‐type PAEs that assemble into 1D crystalline chains, or complex layered crystalline structures of PAEs that alternate in NP core identity (composition or size) (Section .). A second strategy to impart directional interactions between spherical particles involves trapping NPs within or at the vertices of anisotropic DNA origami constructs .…”

“…Finally, the PAEs with programmed valency and directional binding as a result of anisotropic core shape or surface functionalization (Section .) have exhibited several unique lattice arrangements not currently realized in PAEs with isotropic binding, namely 1D and 2D crystals, body‐centered tetragonal (bct) unit cells, layered structures, the Laves phase isostructural to dicopper magnesium (MgCu 2 ), and even diamond symmetry . As these more complex phases indicate, further experimental and theoretical investigations are required to garner a full understanding of the multiple different forces that are important in dictating PAE assembly.…”

Dynamic Nanostructures from DNA‐Coupled Molecules, Polymers, and Nanoparticles

“…However, it is still very challenging to fabricate multicomponent assembly systems where each particle is positioned at the desired locations. Here, we introduce some notable examples of such multicomponent nanostructures . Recently, Mirkin and co‐workers employed template‐confined DNA‐directed assembly to build multicomponent and reconfigurable superlattices of nanoparticles (Figure b) .…”