Altering DNA-Programmable Colloidal Crystallization Paths by Modulating Particle Repulsion.

Colloidal crystal engineering with DNA can be used to realize precise control over nanoparticle (NP) arrangement. Here, we investigate a case of DNA-based assembly where the properties of DNA as a polyelectrolyte brush are employed to alter a hybridization-driven NP crystallization pathway. Using the coassembly of DNA-conjugated proteins and spherical gold nanoparticles (AuNPs) as a model system, we explore how steric repulsion between noncomplementary, neighboring NPs due to overlapping DNA shells can influence their ligand-directed behavior. Specifically, our experimental data coupled with coarse-grained molecular dynamics (MD) simulations reveal that, by changing factors related to NP repulsion, two structurally distinct outcomes can be achieved. When steric repulsion between DNA-AuNPs is significantly greater than that between DNA-proteins, a lower packing density crystal lattice is favored over the structure that is predicted by design rules based on DNA hybridization considerations alone. This is enabled by the large difference in DNA density on AuNPs versus proteins and can be tuned by modulating the flexibility, and thus conformational entropy, of the DNA on the constituent particles. At intermediate ligand flexibility, the crystallization pathways are energetically similar, and the structural outcome can be adjusted using the density of DNA duplexes on DNA-AuNPs and by screening the Coulomb potential between them. Such lattices are shown to undergo dynamic reorganization upon changing the salt concentration. These data help elucidate the structural considerations necessary for understanding repulsive forces in DNA-mediated assembly and lay the groundwork for using them to increase architectural diversity in engineering colloidal crystals.

Modulating Nanoparticle Superlattice Structure Using Proteins with Tunable Bond Distributions.

Herein, we investigate the use of proteins with tunable DNA modification distributions to modulate nanoparticle superlattice structure. Using beta-galactosidase (ßgal) 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: ßgal with uniformly distributed DNA bonding elements results in body-centered cubic crystals, whereas DNA functionalization of cysteines results in AB2 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.

Exploring the zone of anisotropy and broken symmetries in DNA-mediated nanoparticle crystallization.

In this work, we present a joint experimental and molecular dynamics simulations effort to understand and map the crystallization behavior of polyhedral nanoparticles assembled via the interaction of DNA surface ligands. In these systems, we systematically investigated the interplay between the effects of particle core (via the particle symmetry and particle size) and ligands (via the ligand length) on crystallization behavior. This investigation revealed rich phase diagrams, previously unobserved phase transitions in polyhedral crystallization behavior, and an unexpected symmetry breaking in the ligand distribution on a particle surface. To understand these results, we introduce the concept of a zone of anisotropy, or the portion of the phase space where the anisotropy of the particle is preserved in the crystallization behavior. Through comparison of the zone of anisotropy for each particle we develop a foundational roadmap to guide future investigations.

Effect of shape on the self-assembly of faceted patchy nanoplates with irregular shape into tiling patterns.

Recent reports of the synthesis and assembly of faceted nanoplates with a wide range of shapes and composition motivates the possibility of a new class of two-dimensional materials with specific patterns targeted for a host of exciting properties. Yet, studies of how nanoplate shape controls their assembly - knowledge necessary for their inverse design from target structures - has been performed for only a handful of systems. By constructing a general framework in which many known faceted nanoplates may be described in terms of four anisotropy dimensions, we discover design rules to guide future synthesis and assembly. We study via Monte Carlo simulations attractive polygons whose shape is altered systematically under the following four transformations: faceting, pinching, elongation and truncation. We report that (i) faceting leads to regular porous structures (ii) pinching stabilizes complex structures such as dodecagonal quasicrystals (iii) elongation leads to asymmetric phase behavior, where low and high aspect ratio nanoplates self-assemble completely different structures and (iv) low and high degrees of truncation transform a complex self-assembler into a disk-like assembler, providing design ideas that could lead to switchable structures. We provide important insight into how the shape and attractive interactions of a nanoplate can be exploited or designed to target specific classes of structures, including space-filling, porous, and complex tilings.

Self-assembly of Archimedean tilings with enthalpically and entropically patchy polygons.

Considerable progress in the synthesis of anisotropic patchy nanoplates (nanoplatelets) promises a rich variety of highly ordered two-dimensional superlattices. Recent experiments of superlattices assembled from nanoplates confirm the accessibility of exotic phases and motivate the need for a better understanding of the underlying self-assembly mechanisms. Here, we present experimentally accessible, rational design rules for the self-assembly of the Archimedean tilings from polygonal nanoplates. The Archimedean tilings represent a model set of target patterns that (i) contain both simple and complex patterns, (ii) are comprised of simple regular shapes, and (iii) contain patterns with potentially interesting materials properties. Via Monte Carlo simulations, we propose a set of design rules with general applicability to one- and two-component systems of polygons. These design rules, specified by increasing levels of patchiness, correspond to a reduced set of anisotropy dimensions for robust self-assembly of the Archimedean tilings. We show for which tilings entropic patches alone are sufficient for assembly and when short-range enthalpic interactions are required. For the latter, we show how patchy these interactions should be for optimal yield. This study provides a minimal set of guidelines for the design of anisostropic patchy particles that can self-assemble all 11 Archimedean tilings.

Shape alloys of nanorods and nanospheres from self-assembly.

Mixtures of anisotropic nanocrystals promise a great diversity of superlattices and phase behaviors beyond those of single-component systems. However, obtaining a colloidal shape alloy in which two different shapes are thermodynamically coassembled into a crystalline superlattice has remained a challenge. Here we present a joint experimental-computational investigation of two geometrically ubiquitous nanocrystalline building blocks-nanorods and nanospheres-that overcome their natural entropic tendency toward macroscopic phase separation and coassemble into three intriguing phases over centimeter scales, including an AB2-type binary superlattice. Monte Carlo simulations reveal that, although this shape alloy is entropically stable at high packing fraction, demixing is favored at experimental densities. Simulations with short-ranged attractive interactions demonstrate that the alloy is stabilized by interactions induced by ligand stabilizers and/or depletion effects. An asymmetry in the relative interaction strength between rods and spheres improves the robustness of the self-assembly process.

Competition of shape and interaction patchiness for self-assembling nanoplates.

Progress in nanocrystal synthesis and self-assembly enables the formation of highly ordered superlattices. Recent studies focused on spherical particles with tunable attraction and polyhedral particles with anisotropic shape, and excluded volume repulsion, but the effects of shape on particle interaction are only starting to be exploited. Here we present a joint experimental-computational multiscale investigation of a class of highly faceted planar lanthanide fluoride nanocrystals (nanoplates, nanoplatelets). The nanoplates self-assemble into long-range ordered tilings at the liquid-air interface formed by a hexane wetting layer. Using Monte Carlo simulation, we demonstrate that their assembly can be understood from maximization of packing density only in a first approximation. Explaining the full phase behaviour requires an understanding of nanoplate-edge interactions, which originate from the atomic structure, as confirmed by density functional theory calculations. Despite the apparent simplicity in particle geometry, the combination of shape-induced entropic and edge-specific energetic effects directs the formation and stabilization of unconventional long-range ordered assemblies not attainable otherwise.

Pressure driven flow of polymer solutions in nanoscale slit pores.

Polymer solutions subject to pressure driven flow and in nanoscale slit pores are systematically investigated using the dissipative particle dynamics approach. The authors investigated the effect of molecular weight, polymer concentration, and flow rate on the profiles across the channel of the fluid and polymer velocities, polymer density, and the three components of the polymers radius of gyration. They found that the mean streaming fluid velocity decreases as the polymer molecular weight and/or polymer concentration is increased, and that the deviation of the velocity profile from the parabolic profile is accentuated with increase in polymer molecular weight or concentration. They also found that the distribution of polymers conformation is highly anisotropic and nonuniform across the channel. The polymer density profile is also found to be nonuniform, exhibiting a local minimum in the center plane followed by two symmetric peaks. They found a migration of the polymer chains either from or toward the walls. For relatively long chains, as compared to the thickness of the slit, a migration toward the walls is observed. However, for relatively short chains, a migration away from the walls is observed.