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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Preparation and Analysis of RNA Crystals

The crystallization of RiboNucleic Acids (RNA) was studied from the standpoint of mechanisms of crystal growth in three tasks: (1) preparation of high-quality crystals of oligonuclotides for X-ray diffraction, (2) finding pathways to the growth of high-quality crystals for X-ray diffraction and (3) investigation of mechanisms of action of inertial acceleration on crystal growth. In these tasks: (1) RNA crystals were prepared and studied by X-ray diffraction; (2) a pathway to high-quality crystals was discovered and characterized; a combination of kinetic and equilibrium factors could be optimized as described below; and (3) an interplay between purity and gravity was found in a combination of space and ground experiments with nucleic acids and proteins. Most significantly, the rate of concentration of precipitant and RNA can be controlled by membrane-based methods of water removal or by diffusion of multivalent cations across an interface stabilized by a membrane. Oligonucleotide solutions are electrokinetically stabilized colloids, and crystals can form by the controlled addition of multivalent cations.

Todd, Paul↗
DOE OSTI2021

Low-Density 2D Superlattices Assembled via Directional DNA Bonding

It is critical to assemble nanoparticles (NPs) into superlattices with controlled symmetries and spacings on substrates for metamaterials applications, where such structural parameters dictate their properties. Here, we use DNA to assemble anisotropic NPs of three shapes-cubes, octahedra, and rhombic dodecahedra-on substrates and investigate their thermally induced reorganization into two-dimensional (2D) crystalline films. We report two new low-density 2D structures, including a honeycomb lattice based on octahedral NPs. The low-density lattices favored here are not usually seen when particles are crystallized via other bottom-up assembly techniques. Furthermore, we show that, consistent with the complementary contact model, a primary driving force for crystallization is the formation of directional, face-to-face DNA bonds between neighboring NPs and between NPs and the substrate. Finally, our results can be used to deliberately prepare crystalline NP films with novel morphologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Regulating phase behavior of nanoparticle assemblies through engineering of DNA-mediated isotropic interactions

Self-assembly of isotropically interacting particles into desired crystal structures could allow for creating designed functional materials via simple synthetic means. However, the ability to use isotropic particles to assemble different crystal types remains challenging, especially for generating low-coordinated crystal structures. Here, we demonstrate that isotropic pairwise interparticle interactions can be rationally tuned through the design of DNA shells in a range that allows transition from common, high-coordinated FCC-CuAu and BCC-CsCl lattices, to more exotic symmetries for spherical particles such as the SC-NaCl lattice and to low-coordinated crystal structures (i.e., cubic diamond, open honeycomb). The combination of computational and experimental approaches reveals such a design strategy using DNA-functionalized nanoparticles and successfully demonstrates the realization of BCC-CsCl, SC-NaCl, and a weakly ordered cubic diamond phase. The study reveals the phase behavior of isotropic nanoparticles for DNA–shell tunable interaction, which, due to the ease of synthesis is promising for the practical realization of non-close-packed lattices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Controlling morphology in hybrid isotropic/patchy particle assemblies

Brownian dynamics is used to study self-assembly in a hybrid system of isotropic particles (IPs), combined with anisotropic building blocks that represent special “designer particles.” Those are modeled as spherical patchy particles (PPs) with binding only allowed between their patches and IPs. In this study, two types of PPs are considered: Octahedral PPs (Oh-PPs) and Square PPs (Sq-PPs), with octahedral and square arrangements of patches, respectively. The self-assembly is additionally facilitated by the simulated annealing procedure. Here, the resultant structures are characterized by a combination of local correlations in cubatic ordering and a symmetry-specific variation of bond orientation order parameters (SymBOPs). By varying the PP/IP size ratio, we detected a sharp crossover between two distinct morphologies in both types of systems. High symmetry phases, NaCl crystal for Oh-PP and square lattice for Sq-PP, are observed for larger size ratios. For the smaller ones, the dominant morphologies are significantly different, e.g., Oh-PPs form a compact amorphous structure with predominantly face-to-face orientation of neighboring PPs. Unusually, for a morphology without a long-range order, it is still possible to identify well organized coherent clusters of this structure, thanks to the adoption of our SymBOP-based characterization.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Molecular-level understanding of gibbsite particle aggregation in water

Using molecular dynamics simulations, we investigate the molecular scale origin of crystal face selectivity when one gibbsite particle attaches to another in water. A comparison of the free energy per unit surface area of particle–particle attachment indicates that particle attachment through edge surfaces, where the edge surfaces are either (1 0 0) or (1 1 0) crystal faces, is more energetically favorable compared to attachment between two basal surfaces (i.e., (0 0 1) crystal faces) or between the basal surface of one particle and the edge surface of another. This result suggests that gibbsite crystals with low basal/edge surface area ratio will preferentially attach through edge surfaces, potentially helping the crystals grow laterally. However, for larger gibbsite particles (high basal/edge surface area ratio) the total free energy, not normalized by surface area, of particle attachment through the basal surfaces is lower (more negative) than attachment through the edge surfaces, indicating that larger gibbsite particles will preferentially aggregate through basal surface attachments. The short-range electrostatic interactions including the interparticle hydrogen bonds from surface –OH groups drive particle attachment, and the dominant contribution to the free energy minimum is enthalpic rather than entropic. However, the enthalpy of basal-edge attachment is significantly offset by the entropy leading to a higher free energy (less negative) compared to that of basal-basal attachment. Study of the free energy for a few imperfect attachments of two particles indicates a higher free energy (i.e., less negative, less stable), compared to a perfect attachment

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Phonon-mediated lipid raft formation in biological membranes

Short-wavelength collective molecular motions, also known as phonons, have recently attracted much interest in revealing dynamic properties of biological membranes through the use of neutron and x-ray scattering, infrared and Raman spectroscopies, and molecular dynamics simulations. Experimentally detecting unique vibrational patterns such as, shear phonon excitations, viscoelastic crossovers, transverse acoustic phonon gaps, and continuous and truncated optical phonon modes in cellular membranes, to name a few, has proven non-trivial. Here, we review recent advances in liquid thermodynamics that have resulted in the development of the phonon theory of 1 liquids. The theory has important predictions regarding the shear vibrational spectra of fluids, namely the emergence of viscoelastic crossovers and transverse acoustic phonon gaps. Furthermore, we show that these vibrational patterns are common in soft (non-crystalline) materials, including, but not limited to liquids, colloids, liquid crystals (mesogens), block copolymers, and biological membranes. The existence of viscoelastic crossovers and acoustic phonon gaps define the self-diffusion properties of cellular membranes and provide a molecular picture of the transient nature of lipid rafts.1 Importantly, the timescales (picoseconds) for the formation and dissolution of transient lipid rafts match the lifetime of the formation and breakdown of interfacial water hydrogen bonds. Apart from acoustic propagating phonon modes, biological membranes can also support more energetic non-propagating optical phonon excitations, also known as standing waves or breathing modes. Importantly, optical phonons can be truncated due to the existence of finite size nanodomains made up of strongly correlated lipid-cholesterol molecular pairs. These strongly coupled molecular pairs can serve as nucleation centers for the formation of stable rafts at larger length scales, due to correlations of spontaneous fluctuations (Onsager’s regression hypothesis). Finally and importantly, molecular level viscoelastic crossovers, acoustic phonon gaps, and continuous and truncated optical phonon modes may offer insights as to how lipid-lipid and lipid-protein interactions enable biological function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Complex Dirac-like Electronic Structure in Atomic Site-Ordered Rh 3 In 3.4 Ge 3.6

We report the synthesis via an indium flux method of a novel single-crystalline compound Rh 3 In 3.4 Ge 3.6 that belongs to the cubic Ir 3 Ge 7 structure type. In Rh 3 In 3.4 Ge 3.6 , the In and Ge atoms preferentially occupy, respectively, the 12d and 16f sites of the Im3¯m space group, thus creating a colored variant of the Ir 3 Ge 7 structure. Like the other compounds of the Ir 3 Ge 7 family, Rh 3 In 3.4 Ge 3.6 shows potential as a thermoelectric, displaying a relatively large power factor, PF ~ 2 mW/cm K 2 , at a temperature T ~ 225 K, albeit showing a modest figure of merit, ZT = 8 x 10 -4 , because of the lack of a finite band gap. These figures might improve through a use of chemical substitution strategies to achieve band gap opening. Remarkably, electronic band structure calculations reveal that this compound displays a complex Dirac-like electronic structure relatively close to the Fermi level. The electronic structure is composed of several Dirac type-I and type-II nodes, and even Dirac type-III nodes that result from the touching between a flat band and a linearly dispersing band. Here, this rich Dirac-like electronic dispersion suggests the possibility to observe experimentally Dirac type-III nodes and study their role in the physical properties of Rh 3 In 3.4 Ge 3.6 and related Ir 3 Ge 7 -type materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nanocrystal Assemblies: Current Advances and Open Problems

Here we explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Symmetry-specific orientational order parameters for complex structures

A comprehensive framework of characterizing complex self-assembled structures with a set of orientational order parameters is presented. It is especially relevant in the context of using anisotropic building blocks with various symmetries. Two classes of tensor order parameters are associated with polyhedral nematic and bond orientational order. For the latter, a variation of classical bond order parameters (BOPs) is introduced, which takes advantage of the symmetry of constituent particles and/or expected crystalline phases. These symmetrized BOPs can be averaged over an entire system or assigned locally to an individual bond. By combining that with the bond percolation procedure, one is able to identify coherent domains within a self-assembled structure. As a demonstration of the proposed framework, we apply it to a simulated hybrid system that combines isotropic and patchy particles with octahedral symmetry. In conclusion, not only does the methodology allow one to identify individual crystalline domains but also it detects coherent clusters of a peculiar compact amorphous structure that is not space-filling and lacks any long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photo-printing of faceted DNA patchy particles

Patchy particles with shape complementarity can serve as building blocks for assembling colloidal superstructures. Alternatively, encoding information on patches using DNA can direct assembly into a variety of crystalline or other preprogrammed structures. Here, we present a tool where DNA is used both to engineer shape and to encode information on colloidal particles. Two reactive oil emulsions with different but complementary DNA (cDNA) brushes are assembled into CsCl-like crystalline lattices. The DNA brushes are recruited to and ultimately localized at the junctions between neighboring droplets, which gives rise to DNA-encoded faceted patches. The emulsions are then solidified by ultraviolet (UV) polymerization, producing faceted patchy particles. The facet size and DNA distribution are determined by the balance between the DNA binding energy and the elastic deformation energy of droplets. This method leads to a variety of new patchy particles with directional interactions in scalable quantities.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote—and, in some cases, may be necessary for—the self-assembly of a binary cocrystal. Using computer simulations, we identify two mechanisms responsible for this phenomenon. First, excess small particles act like plasticizers and enable systems to reach a greater supersaturation before kinetic arrest occurs. Second, they can disfavor competing structures that may interfere with the growth of the target structure. We find the phase behavior of simulated mixtures of nearly hard spheres closely matches published experimental results. We demonstrate the generality of our findings for mixtures of particles of arbitrary shape by presenting a binary mixture of hard shapes that only self-assembles with an excess of the smaller component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nanoparticle self-assemblies with modern complexity

Thanks to decades of tireless efforts, nanoparticle assemblies have reached at an extremely high level of controllability, sophistication, and complexity, with new insights provided by integration with graph theory, cutting-edge characterization, and machine learning (ML)-based computation and modeling, as well as with ever-diversifying applications in energy, catalysis, biomedicine, optics, electronics, magnetics, organic biosynthesis, and quantum technology. Nanoparticle assemblies can be crystalline, known as superlattices or supracrystals. Their assembly entails a transition from disorder—dispersed nanoparticles—to order, which can be achieved through classical nucleation pathways or nonclassical pathways via prenucleation precursors or particle aggregation. Further, the periodic lattices allow facile manipulations of electrons, phonons, photons, and even spins, leading to advanced device components and metamaterials. Meanwhile, aperiodic assemblies out of nanoparticles, such as gels, networks, and amorphous solids, also start to attract attentions. Despite the loss of periodicity, symmetry-lowering or symmetry-breaking three-dimensional (3D) structures emerge with unique properties, such as chiroptical activity, topological mechanical strength, and quantum entanglement. Real-space imaging such as electron microscopy and X-ray based tomography methods are utilized to characterize these complex structures, while mathematical tools such as graph theories are in need to describe such complex structures. This issue aims to provide a timely review of the efforts in this greatly broadened materials design space including experiment, simulation, theory, and applications. Nine top experts (and their teams) from four countries deliver six review papers, summarizing fundamental mechanistic understandings of nanoparticle assemblies, highlighted with the developments of state-of-the-art in situ characterization tools and ML-assisted reverse engineering, and newly emergent applications of nanoarchitectures.

36 MATERIALS SCIENCE↗
NASA NTRS2005

Electrohydrodynamic Flows in Electrochemical Systems

Recent studies have established a new class of assembly processes with colloidal suspensions. Particles are driven together to form large crystalline structures in both dc and ac fields. The current work centers on this new class of flows in ac fields. In the research carried out under the current award, it was established that: (i) Small colloidal particles crystallize near an electrode due to electrohydrodynamic flows induced by an sinusoidally varying applied potential. (ii) These flows originate due to disturbances in the electrode polarization layer arising from the presence of the particles. Inasmuch as the charge and the field strength both scale on the applied field, the flows are proportional to the square of the applied voltage. (iii) Suspensions of two different sorts of particles can be crystallized and will form well-ordered binary crystals. (iv) At high frequencies the EHD flows die out. Thus, with a homogeneous system the particles become widely spaced due to dipolar repulsion. With a binary suspension, however, the particles may become attractive due to dipolar attraction arising from differences in electrokinetic dipoles. Consequently binary crystals form at both high and low frequencies.

Saville, D. A.↗
NASA NTRS1999

Binary Colloidal Alloy Test Conducted on Mir

Colloids are tiny (submicron) particles suspended in fluid. Paint, ink, and milk are examples of colloids found in everyday life. The Binary Colloidal Alloy Test (BCAT) is part of an extensive series of experiments planned to investigate the fundamental properties of colloids so that scientists can make colloids more useful for technological applications. Some of the colloids studied in BCAT are made of two different sized particles (binary colloidal alloys) that are very tiny, uniform plastic spheres. Under the proper conditions, these colloids can arrange themselves in a pattern to form crystals. These crystals may form the basis of new classes of light switches, displays, and optical devices. Windows made of liquid crystals are already in the marketplace. These windows change their appearance from transparent to opaque when a weak electric current is applied. In the future, if the colloidal crystals can be made to control the passage of light through them, such products could be made much more cheaply. These experiments require the microgravity environment of space because good quality crystals are difficult to produce on Earth because of sedimentation and convection in the fluid. The BCAT experiment hardware included two separate modules for two different experiments. The "Slow Growth" hardware consisted of a 35-mm camera with a 250- exposure photo film cartridge. The camera was aimed toward the sample module, which contained 10 separate colloid samples. A rack of small lights provided backlighting for the photographs. The BCAT hardware was launched on the shuttle and was operated aboard the Russian space station Mir by American astronauts John Blaha and David Wolf (launched September 1996 and returned January 1997; reflown September 1997 and returned January 1998). To begin the experiment, one of these astronauts would mix the samples to disperse the colloidal particles and break up any crystals that might have already formed. Once the samples were mixed and the experiment was powered on, the hardware operated autonomously, taking photos of the colloidal samples over a 90-day period.

Hoffmann, Monica I.↗
DOE OSTI2022

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ligand-Mediated Phase Control in Colloidal AgInSe 2 Nanocrystals

Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe 2 nanocrystals can be achieved by performing reactions in the presence, or absence, of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in formation of metastable AgInSe 2 nanocrystals, as they mediate in-situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe 2 . We pro-vide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe 2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe 2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag 2 Se nanocrystal intermediates convert through kinetically slow, non-topotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe 2 . Furthermore, on the basis of these discoveries, we offer new insight into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗