Modulating Nanoparticle Superlattice Structure Using Proteins with Tunable Bond Distributions

Abstract

Herein, we investigate the use of proteins with tunable DNA modification distributions to modulate nanoparticle superlattice structure. Using beta-galactosidase (βgal) as a model system, we have employed the orthogonal chemical reactivities of surface amines and thiols to synthesize protein-DNA conjugates with 36 evenly distributed or 8 specifically positioned oligonucleotides. When these are assembled into crystalline superlattices with gold nanoparticles, we find that the distribution of DNA modifications modulates the favored structure: βgal with uniformly distributed DNA bonding elements results in body-centered cubic crystals, whereas DNA functionalization of cysteines results in AB packing. We probe the role of protein oligonucleotide number and conjugate size on this observation, which revealed the importance of oligonucleotide distribution in this observed assembly behavior. These results indicate that proteins with defined DNA modification patterns are powerful tools for controlling nanoparticle superlattices architecture, and establish the importance of oligonucleotide distribution in the assembly behavior of protein-DNA conjugates.

Particle analogs of electrons in colloidal crystals

“…However, in the science of colloidal crystals, in which particles are often analogized with atoms, a particle analog to electrons has not been invoked, despite the synthesis of hundreds of colloidal crystals and the development of certain approaches into elaborate forms of crystal engineering (9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). In particular, colloidal crystal engineering with DNA has led to the design of structures with diverse symmetries, lattice parameters, and crystal habits (12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22). However, to date, the particles modified with DNA that define such structures behave as programmable atom equivalents (PAEs) and have fixed particle positions at set stoichiometric ratios.…”

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 .).…”

Hamilton Receptor‐Mediated Self‐Assembly of Orthogonally Functionalized Au and TiO2 Nanoparticles

“…[9] Depending on the ligand coverage, the self-assembly of superlattices with translational and orientational order can even be tunable. [10] In this context, supramolecular assembly concepts have found numerous applications for the molecular-controlled bottom-up synthesis of functional hybrid materials, [11 -13] organized superlattices, [14,15] and highperformance alloys. [16] In this context, composite materials consisting of Au nanoparticles firmly embedded in titanium dioxide (TiO 2 ) have proven their viability in a variety of application areas, including dye-sensitized solar cells (DSSCs), [17,18] catalysis, [19] biosensors, [20,21] and many more over the last decade.…”