Colloidal quasicrystals engineered with DNA.

In principle, designing and synthesizing almost any class of colloidal crystal is possible. Nonetheless, the deliberate and rational formation of colloidal quasicrystals has been difficult to achieve. Here we describe the assembly of colloidal quasicrystals by exploiting the geometry of nanoscale decahedra and the programmable bonding characteristics of DNA immobilized on their facets. This process is enthalpy-driven, works over a range of particle sizes and DNA lengths, and is made possible by the energetic preference of the system to maximize DNA duplex formation and favour facet alignment, generating local five- and six-coordinated motifs. This class of axial structures is defined by a square-triangle tiling with rhombus defects and successive on-average quasiperiodic layers exhibiting stacking disorder which provides the entropy necessary for thermodynamic stability. Taken together, these results establish an engineering milestone in the deliberate design of programmable matter.

Accurate computational design of three-dimensional protein crystals.

Protein crystallization plays a central role in structural biology. Despite this, the process of crystallization remains poorly understood and highly empirical, with crystal contacts, lattice packing arrangements and space group preferences being largely unpredictable. Programming protein crystallization through precisely engineered side-chain-side-chain interactions across protein-protein interfaces is an outstanding challenge. Here we develop a general computational approach for designing three-dimensional protein crystals with prespecified lattice architectures at atomic accuracy that hierarchically constrains the overall number of degrees of freedom of the system. We design three pairs of oligomers that can be individually purified, and upon mixing, spontaneously self-assemble into >100 µm three-dimensional crystals. The structures of these crystals are nearly identical to the computational design models, closely corresponding in both overall architecture and the specific protein-protein interactions. The dimensions of the crystal unit cell can be systematically redesigned while retaining the space group symmetry and overall architecture, and the crystals are extremely porous and highly stable. Our approach enables the computational design of protein crystals with high accuracy, and the designed protein crystals, which have both structural and assembly information encoded in their primary sequences, provide a powerful platform for biological materials engineering.

Design Principles for Using Amphiphilic Polymers To Create Microporous Water.

Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores─referred to as "microporous water"─enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components─including catalysts, proteins, and cells─while retaining as much of their internal pore volume as possible. Here, we establish design principles for the noncovalent surface functionalization of hydrophobic metal-organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal-organic framework particles in aqueous environments to augment the properties of microporous water.

Hints of Growth Mechanism Left in Supercrystals.

Supercrystals of DNA-functionalized nanoparticles are visualized in three dimensions using X-ray ptychographic tomography, and their reciprocal spaces are mapped with small-angle X-ray scattering in order to better understand their internal defect structures. X-ray ptychographic tomography reveals various types of defects in an assembly that otherwise exhibits a single crystalline diffraction pattern. On average, supercrystals composed of smaller nanoparticles are smaller in size than supercrystals composed of larger particles. Additionally, supercrystals composed of small nanoparticles are typically aggregated into larger "necklace-like" structures. Within these larger structures, some but not all pairs of connected domains are coherent in their relative orientations. In contrast, supercrystals composed of larger nanoparticles with longer DNA ligands typically form faceted crystals. The combination of these two complementary X-ray techniques reveals that the crystalline assemblies grow by aggregation of smaller assemblies followed by rearrangement of nanoparticles.

Higher-Order VLP-Based Protein Macromolecular Framework Structures Assembled via Coiled-Coil Interactions.

Hierarchical organization is one of the fundamental features observed in biological systems that allows for efficient and effective functioning. Virus-like particles (VLPs) are elegant examples of a hierarchically organized supramolecular structure, where many subunits are self-assembled to generate the functional cage-like architecture. Utilizing VLPs as building blocks to construct two- and three-dimensional (3D) higher-order structures is an emerging research area in developing functional biomimetic materials. VLPs derived from P22 bacteriophages can be repurposed as nanoreactors by encapsulating enzymes and modular units to build higher-order catalytic materials via several techniques. In this study, we have used coiled-coil peptide interactions to mediate the P22 interparticle assembly into a highly stable, amorphous protein macromolecular framework (PMF) material, where the assembly does not depend on the VLP morphology, a limitation observed in previously reported P22 PMF assemblies. Many encapsulated enzymes lose their optimum functionalities under the harsh conditions that are required for the P22 VLP morphology transitions. Therefore, the coiled-coil-based PMF provides a fitting and versatile platform for constructing functional higher-order catalytic materials compatible with sensitive enzymes. We have characterized the material properties of the PMF and utilized the disordered PMF to construct a biocatalytic 3D material performing single- and multistep catalysis.

Surface Functional Groups Affect Iron (Hydr)oxide Heterogeneous Nucleation: Implications for Membrane Scaling.

Because of its favorable thermodynamics and fast kinetics, heterogeneous solid nucleation on membranes triggers early-stage mineral scaling. Iron (hydr)oxide, a typical membrane scale, initially forms as nanoparticles that interact with surface functional groups on membranes, but these nanoscale phenomena are difficult to observe in real time. In this study, we utilized in situ grazing incidence small angle X-ray scattering and ex situ atomic force microscopy to examine the heterogeneous nucleation of iron (hydr)oxide on surface functional groups commonly used in membranes, including hydroxyl (OH), carboxyl (COOH), and fluoro (F) groups. We found that, compared to nucleation on hydrophilic OH- and COOH-surfaces, the high hydrophobicity of an F-modified surface significantly reduced the extents of both heterogeneously and homogeneously formed iron (hydr)oxide nucleation. Moreover, on the OH-surface, the high functional group density of 0.76 nmol/cm2 caused faster heterogeneous nucleation than that on a COOH-surface, with a density of 0.28 ± 0.04 nmol/cm2. The F-surface also had the highest heterogeneous nucleation energy barrier (26 ± 0.6 kJ/mol), followed by COOH- (23 ± 0.8 kJ/mol) and OH- (20 ± 0.9 kJ/mol) surfaces. The kinetic and thermodynamic information provided here will help us better predict the rates and extents of early-stage scaling of iron (hydr)oxide nanoparticles in membrane processes.

Impact of peripheral alkyl chain length on mesocrystal assemblies of G2 dendrons.

Unique sphere-packing mesophases such as Frank-Kasper (FK) phases have emerged from the viable design of intermolecular interactions in supramolecular assemblies. Herein, a series of Cn-G2-CONH2 dendrons possessing an identical core wedge are investigated to elucidate the impact of peripheral alkyl chain lengths (Cn) on the formation of the close-packed structures. The C18 and C14 dendrons, of which the contour lengths of the periphery Lp are longer than the wedge length Lw, assemble into a uniform sphere-packing phase such as body-centred cubic (BCC), whereas the C8 dendron with short (Lp < Lw) corona environment forms the FK A15 phase. Particularly in the intermediate C12 and C10 dendrons (Lp ≈ Lw), cooling the samples from an isotropic state leads to cooling-rate-dependent phase behaviours. The C12 dendron produces two structures of hexagonal columnar and sphere-packing phases (BCC and A15), while the C10 dendron generates the A15 and σ phases by the fast- and slow-cooling processes, respectively. Our results show the impact of peripheral alkyl chain lengths on the formation of mesocrystal phases, where the energy landscape of the dendrons at Lp/Lw ≈ 1 must be more complex and delicate than those with either longer or shorter peripheral alkyl chains.

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels.

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. To understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV-vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

Symmetry-Breaking Dendrimer Synthons in Colloidal Crystal Engineering with DNA.

Breaking symmetry in colloidal crystals is challenging due to the inherent chemical and structural isotropy of many nanoscale building blocks. If a non-particle component could be used to anisotropically encode such building blocks with orthogonal recognition properties, one could expand the scope of structural and compositional possibilities of colloidal crystals beyond what is thus far possible with purely particle-based systems. Herein, we report the synthesis and characterization of novel DNA dendrimers that function as symmetry-breaking synthons, capable of programming anisotropic and orthogonal interactions within colloidal crystals. When the DNA dendrimers have identical sticky ends, they hybridize with DNA-functionalized nanoparticles to yield three distinct colloidal crystals, dictated by dendrimer size, including a structure not previously reported in the field of colloidal crystal engineering, Si2Sr. When used as symmetry-breaking synthons (when the sticky ends deliberately consist of orthogonal sequences), the synthesis of binary and ternary colloidal alloys with structures that can only be realized through directional interactions is possible. Furthermore, by modulating the extent of shape anisotropy within the DNA dendrimers, the local distribution of the nanoparticles within the crystals can be directed.

Apex hydrogen bonds in dendron assemblies modulate close-packed mesocrystal structures.

The close-packed mesocrystal structures from soft-matter assemblies have recently received attention due to their structural similarity to atomic crystals, displaying various sphere-packing Frank-Kasper (FK) and quasicrystal structures. Herein, diverse mesocrystal structures are explored in second-generation dendrons (G2-X) designed with identical wedges, in which the terminal functionalities X = CONH2 and CH2NH2 represent two levels of the strong and weak hydrogen-bonding apexes, respectively. The cohesive interactions at the core apex, referred to as the core interactions, are effectively modulated by forming heterogeneous hydrogen bonds between these two functional units. For the dendron assemblies compositionally close to each pure component of G2-CONH2 and G2-CH2NH2, their own FK A15 and C14 phases dominate other phases, respectively. We show the existence of the wide-range FK σ including the dodecagonal quasicrystal (DDQC) phases from the dendron mixtures between G2-CONH2 and G2-CH2NH2, providing an experimental phase sequence of A15-σ-DDQC-C14 as the core interactions are alleviated. Intriguingly, the temperature dependence of particle sizes shows that the high plateau values of particle sizes are maintained equivalently until each threshold temperature (Tth), followed by a prompt decrease above the Tth. A decrease in Tth by alleviating the core interactions and its composition dependence suggest that the more size-dispersed particles, the more susceptibility to chain exchange with increasing temperature. Our results on the formation of supramolecular dendron assemblies provide a guide to understand the core-interaction-dependent mesocrystal structures toward the fundamental principle underlying the temperature dependence of their particle sizes.

Open-channel metal particle superlattices.

Although tremendous advances have been made in preparing porous crystals from molecular precursors1,2, there are no general ways of designing and making topologically diversified porous colloidal crystals over the 10-1,000 nm length scale. Control over porosity in this size range would enable the tailoring of molecular absorption and storage, separation, chemical sensing, catalytic and optical properties of such materials. Here, a universal approach for synthesizing metallic open-channel superlattices with pores of 10 to 1,000 nm from DNA-modified hollow colloidal nanoparticles (NPs) is reported. By tuning hollow NP geometry and DNA design, one can adjust crystal pore geometry (pore size and shape) and channel topology (the way in which pores are interconnected). The assembly of hollow NPs is driven by edge-to-edge rather than face-to-face DNA-DNA interactions. Two new design rules describing this assembly regime emerge from these studies and are then used to synthesize 12 open-channel superlattices with control over crystal symmetry, channel geometry and topology. The open channels can be selectively occupied by guests of the appropriate size and that are modified with complementary DNA (for example, Au NPs).

Shape memory in self-adapting colloidal crystals.

Reconfigurable, mechanically responsive crystalline materials are central components in many sensing, soft robotic, and energy conversion and storage devices1-4. Crystalline materials can readily deform under various stimuli and the extent of recoverable deformation is highly dependent upon bond type1,2,5-10. Indeed, for structures held together via simple electrostatic interactions, minimal deformations are tolerated. By contrast, structures held together by molecular bonds can, in principle, sustain much larger deformations and more easily recover their original configurations. Here we study the deformation properties of well-faceted colloidal crystals engineered with DNA. These crystals are large in size (greater than 100 µm) and have a body-centred cubic (bcc) structure with a high viscoelastic volume fraction (of more than 97%). Therefore, they can be compressed into irregular shapes with wrinkles and creases, and, notably, these deformed crystals, upon rehydration, assume their initial well-formed crystalline morphology and internal nanoscale order within seconds. For most crystals, such compression and deformation would lead to permanent, irreversible damage. The substantial structural changes to the colloidal crystals are accompanied by notable and reversible optical property changes. For example, whereas the original and structurally recovered crystals exhibit near-perfect (over 98%) broadband absorption in the ultraviolet-visible region, the deformed crystals exhibit significantly increased reflection (up to 50% of incident light at certain wavelengths), mainly because of increases in their refractive index and inhomogeneity.

Porous but Mechanically Robust All-Inorganic Antireflective Coatings Synthesized using Polymers of Intrinsic Microporosity.

Here, we introduce polymer of intrinsic microporosity 1 (PIM-1) to design single-layer and multilayered all-inorganic antireflective coatings (ARCs) with excellent mechanical properties. Using PIM-1 as a template in sequential infiltration synthesis (SIS), we can fabricate highly uniform, mechanically stable conformal coatings of AlOx with porosities of ∼50% and a refractive index of 1.41 compared to 1.76 for nonporous AlOx that is perfectly suited for substrates commonly used in high-end optical systems or touch screens (e.g., sapphire, conductive glass, bendable glass, etc.). We show that such films can be used as a single-layer ARC capable of reduction of the Fresnel reflections of sapphire to as low as 0.1% at 500 nm being deposited only on one side of the substrate. We also demonstrate that deposition of the second layer with higher porosity using block copolymers enables the design of graded-index double-layered coatings. AlOx structures with just two layers and a total thickness of less than 200 nm are capable of reduction of Fresnel reflections under normal illumination to below 0.5% in a broad spectral range with 0.1% reflection at 700 nm. Additionally, and most importantly, we show that highly porous single-layer and graded-index double-layered ARCs are characterized by high hardness and scratch resistivity. The hardness and the maximum reached load were 7.5 GPa and 13 mN with a scratch depth of about 130 nm, respectively, that is very promising for the structures consisting of two porous AlOx layers with 50% and 85% porosities, correspondingly. Such mechanical properties of coatings can also allow their application as protective layers for other optical coatings.

Multilayered Ordered Protein Arrays Self-Assembled from a Mixed Population of Virus-like Particles.

Biology shows many examples of spatially controlled assembly of cells and biomacromolecules into hierarchically organized structures, to which many of the complex biological functions are attributed. While such biological structures have inspired the design of synthetic materials, it is still a great challenge to control the spatial arrangement of individual building blocks when assembling multiple types of components into bulk materials. Here, we report self-assembly of multilayered, ordered protein arrays from mixed populations of virus-like particles (VLPs). We systematically tuned the magnitude of the surface charge of the VLPs via mutagenesis to prepare four different types of VLPs for mixing. A mixture of up to four types of VLPs selectively assembled into higher-order structures in the presence of oppositely charged dendrimers during a gradual lowering of the ionic strength of the solution. The assembly resulted in the formation of three-dimensional ordered VLP arrays with up to four distinct layers including a central core, with each layer comprising a single type of VLP. A coarse-grained computational model was developed and simulated using molecular dynamics to probe the formation of the multilayered, core-shell structure. Our findings establish a simple and versatile bottom-up strategy to synthesize multilayered, ordered materials by controlling the spatial arrangement of multiple types of nanoscale building blocks in a one-pot fabrication.

Flexible 3D Nanonetworked Silica Film as a Polymer-Free Drug-Eluting Stent Platform to Effectively Suppress Tissue Hyperplasia in Rat Esophagus.

Loading and eluting drugs on self-expandable metallic stents (SEMSs) can be challenging in terms of fabrication, mechanical stability, and therapeutic effects. In this study, a flexible 3D nanonetworked silica film (NSF) capable of withstanding mechanical stress during dynamic expansion is constructed to function as a drug delivery platform on an entire SEMS surface. Despite covering a broad curved area, the synthesized NSF is defect-free and thin enough to increase the stent strut diameter (110 µm) by only 0.4 percent (110.45 µm). The hydrophobic modification of the surface enables loading of 4.7 times the sirolimus (SRL) concentration in NSF than Cypher, polymer-coated commercial stent, which is based on the same thickness of coating layer. Furthermore, SRL-loaded NSF exhibits a twofold delay in release compared to the control group without NSF. The SRL-loaded NSF SEMS significantly suppresses stent-induced tissue hyperplasia than the control SEMS in the rat esophagus (all variables, p < 0.05). Thus, the developed NSF is a promising polymer-free drug delivery platform to efficiently treat esophageal stricture.

Process-Specific Effects of Sulfate on CaCO3 Formation in Environmentally Relevant Systems.

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO3's formation and is seldom found to significantly affect multiple CaCO3 formation processes. Here, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO3 precursors and nuclei, promoting CaCO3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO3. Meanwhile, adsorbed sulfate on CaCO3 nuclei may poison the surface of smaller CaCO3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.

Structural Changes during the Conversion Reaction of Tungsten Oxide Electrodes with Tailored, Mesoscale Porosity.

In-plane tungsten oxide nanostructures, including hexagonally patterned cylinders and holes in a matrix, were fabricated via sequential infiltration synthesis (SIS) on self-assembled block copolymer templates. Using the tailored morphology and porosity of these model electrodes with in situ grazing incidence small-angle X-ray scattering, the intrinsic structural change of nanoscale active materials during the conversion reaction of WO3 + 6Li ↔ W + 3Li2O was investigated at controlled electrochemical conditions. Reversible electrode volume expansion and contraction was observed during lithiation and delithiation cycles, respectively. The potential where the electrode's thickness expansion started was ∼1.6 V, which is close to the thermodynamically expected one for the conversion reaction of WO3 with lithium (1.65 V). The temporal evolution of the electrode volume at constant electrode potentials revealed high overpotential for bulk lithiation and slow conversion reaction kinetics, despite the tailored porosity of the SIS electrodes. Oxide cylinders showed a smaller overall electrode thickness change, likely due to unconstrained lateral volume change, as compared to a matrix with holes. On the other hand, better connectivity and guided volume change of the latter electrode morphology provided improved cycling stability. In addition, heterogeneity in an electrode, from internal pores and density gradients, was found to aggravate the fragmentation of the electrode during the conversion reaction. Insights into oxide conversion reaction kinetics and the relationship between electrode mesostructure and cycling behavior obtained from this study can help guide the more rational design of conversion electrodes for high-performing batteries.

Confined Growth of DNA-Assembled Superlattice Films.

We study the assembly of DNA-functionalized nanocubes under lateral confinement in microscale square trenches on a DNA-functionalized substrate. Microfocus small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are used to characterize the superlattices (SLs). The results indicate that nanocubes form simple-cubic SLs with square-prism morphology and a (100) out-of-plane orientation to maximize DNA bonding. In-plane, SLs align with the template, exposing their {100} side facets, and the degree of alignment depends on trench size. Interestingly, the distribution of in-plane orientations determined from SAXS and SEM do not agree, indicating that the internal and external structures of the SLs differ. To understand this discrepancy, X-ray ptychography is employed to image the internal structures of the SLs, revealing that SLs which appear to be single-crystalline in SEM may have subsurface grain boundaries, depending on trench size. SEM reveals that the SLs grow via nucleation and growth of randomly oriented domains, which then coalesce; this mechanism explains the observed dependence of alignment and defect structure on size. Interestingly, crystallization occurs via an unusual growth mode, whereby continuous SL layers grow on top of several misoriented islands. Overall, this work elucidates the effect of lateral confinement on the crystallization of DNA-functionalized nanoparticles and shows how X-ray ptychography can be used to gain insight into nanoparticle crystallization.

Understanding Relationships between Free Volume and Oxygen Absorption in Ionic Liquids.

Understanding the factors that govern gas absorption in ionic liquids is critical to the development of high-capacity solvents for catalysis, electrochemistry, and gas separations. Here, we report experimental probes of liquid structure that provide insights into how free volume impacts the O2 absorption properties of ionic liquids. Specifically, we establish that isothermal compressibility─measured rapidly and accurately through small-angle X-ray scattering─reports on the size distribution of transient voids within a representative series of ionic liquids and is correlated with O2 absorption capacity. Additionally, O2 absorption capacities are correlated with thermal expansion coefficients, reflecting the beneficial effect of weak intermolecular interactions in ionic liquids on free volume and gas absorption capacity. Molecular dynamics simulations show that the void size distribution─in particular, the probability of forming larger voids within an ionic liquid─has a greater impact on O2 absorption than the total free volume. These results establish relationships between the ionic liquid structure and gas absorption properties that offer design strategies for ionic liquids with high gas solubilities.

Small-Angle X-ray Scattering Analysis of Colloidal Crystals and Replica Materials Made from l-Arginine-Stabilized Silica Nanoparticles.

Colloidal crystals made from sub-100 nm silica nanoparticles have provided a versatile platform for the template-assisted synthesis of three-dimensionally interconnected semiconducting, metallic, and magnetic replicas. However, the detailed structure of these materials has not yet been characterized. In this study, we investigated the structures of colloidal crystalline films and germanium replicas by scanning electron microscopy and small angle X-ray scattering. The structures of colloidal crystals made by evaporative assembly depends on the size of l-arginine-capped silica nanoparticles. Particles smaller than ∼31 nm diameter assemble into non-close-packed arrangements (bcc) whereas particles larger than 31 nm assemble into random close-packed structures with disordered hexagonal phase. Polycrystalline films of these materials retain their structures and long-range order upon infiltration at high temperature and pressure, and the structure is preserved in Ge replicas. The shear force during deposition and dispersity of silica nanoparticles contributes to the size-based variation in the structure and to the size of crystal domains in the colloidal crystal films.