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Results for “Directed self assembly”

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 721 records · Page 40

Integrated nanotechnology platform for tumor-targeted multimodal imaging and therapeutic cargo release

A major challenge of targeted molecular imaging and drug delivery in cancer is establishing a functional combination of ligand-directed cargo with a triggered release system. Here we develop a hydrogel-based nanotechnology platform that integrates tumor targeting, photon-to-heat conversion, and triggered drug delivery within a single nanostructure to enable multimodal imaging and controlled release of therapeutic cargo. In proof-of-concept experiments, we show a broad range of ligand peptide-based applications with phage particles, heat-sensitive liposomes, or mesoporous silica nanoparticles that self-assemble into a hydrogel for tumor-targeted drug delivery. Because nanoparticles pack densely within the nanocarrier, their surface plasmon resonance shifts to near-infrared, thereby enabling a laser-mediated photothermal mechanism of cargo release. We demonstrate both noninvasive imaging and targeted drug delivery in preclinical mouse models of breast and prostate cancer. Finally, we applied mathematical modeling to predict and confirm tumor targeting and drug delivery. We conclude that these results are meaningful steps toward the design and initial translation of an enabling nanotechnology platform with potential for broad clinical applications.

60 APPLIED LIFE SCIENCES↗

CpoS-Inc interactions facilitate host cell modulation during Chlamydia trachomatis infection

ABSTRACT Chlamydia trachomatis ( C.t .), the leading bacterial cause of sexually transmitted infections, replicates within a unique intracellular compartment called the inclusion, which is modified by secreted proteins known as inclusion membrane (Inc) proteins. Here, we further characterize CpoS, an Inc protein previously shown to be critical for bacterial replication and inclusion development. We demonstrate that CpoS directly binds multiple coiled-coil region-containing Incs and engages Rab GTPases at a separate site. Notably, CpoS-InaC interactions facilitate the recruitment of select Arf GTPases to the inclusion membrane, while Rab recruitment occurs independently of these interactions. Biochemical and biophysical analyses revealed that Incs self-oligomerize to form higher-ordered structures, with CpoS adopting a tetrameric conformation resembling that of eukaryotic SNARE proteins. We propose that these assemblies serve as scaffolds to orchestrate vesicle docking, tethering, and fusion. Our findings highlight the intricate interplay between bacterial and host factors, revealing how C.t . leverages both Inc-Inc interactions and host protein engagement to manipulate vesicular trafficking and sustain infection.

Tijerina, Xavier [Department of Microbiology and I↗

Directed assembly of hybrid nanostructures using optically resonant nanotweezers

This represents the final report for this project. Over the course of the project we have made significant progress in photonically driven nano-assembly including: (1) demonstrating the first direct optical tweezer based manipulation of proteins, (2) the ability to apply optical angular torques to microtubuals and other rod-shaped microparticles, (3) direct assembly of hybrid nanostructures comprising of polymeric nanoparticles and carbon nanotubes and, (4) the ability to drive biological reactions (specifically protein aggregation) that are thermodynamically unfavorable by applying localized optical work. These advancements are described in the list of papers provided in section 2.0 of the below. Summary details are provided in prior year annual reports. We have two additional papers which will be submitted shortly based on the work done under this award. An updated publication list will be provided to the program manager when those are accepted. In this report, we report on a new advancement made in the final project year, which uses the nanotweezer technology to perform direct measurements of particle-surface interactions. Briefly, these measurements are important for characterizing the stability and behavior of colloidal and nanoparticle suspensions and current techniques are limited in their ability to measure piconewton scale interaction forces on sub-micrometer particles due to signal detection limits and thermal noise. In this project year we developed a new technique called “Nanophotonic Force Microscopy” which uses the localized region of exponentially decaying, near-field, light to confine small particles close to a surface. From the statistical distribution of the light intensity scattered by the particle the technique maps out the potential well of the trap and directly quantify the repulsive force between the nanoparticle and the surface. The major advantage of the technique is that it can measure forces and energy wells below the thermal noise limit, resolving interaction forces smaller than 1 pN on dielectric particles as small as 100 nm in diameter.

36 MATERIALS SCIENCE↗

Persistence length regulates emergent dynamics in active roller ensembles

Active colloidal fluids, biological and synthetic, often demonstrate complex self-organization and the emergence of collective behavior. Spontaneous formation of multiple vortices has been recently observed in a variety of active matter systems, however, the generation and tunability of the active vortices not controlled by geometrical confinement remain challenging. Here, we exploit the persistence length of individual particles in ensembles of active rollers to tune the formation of vortices and to orchestrate their characteristic sizes. We use two systems and employ two different approaches exploiting shape anisotropy or polarization memory of individual units for control of the persistence length. We characterize the dynamics of emergent multi-vortex states and reveal a direct link between the behavior of the persistence length and properties of the emergent vortices. We further demonstrate common features between the two systems including anti-ferromagnetic ordering of the neighboring vortices and active turbulent behavior with a characteristic energy cascade in the particles velocity field energy spectra. Finally, our findings provide insights into the onset of spatiotemporal coherence in active roller systems and suggest a control knob for manipulation of dynamic self-assembly in active colloidal ensembles.

42 ENGINEERING↗

Recent Advances in Vertically Aligned Nanocomposites with Tunable Optical Anisotropy: Fundamentals and Beyond

Developing reliable and tunable metamaterials is fundamental to next-generation optical-based nanodevices and computing schemes. In this review, an overview of recent progress made with a unique group of ceramic-based functional nanocomposites, i.e., vertically aligned nanocomposites (VANs), is presented, with the focus on the tunable anisotropic optical properties. Using a self-assembling bottom-up deposition method, the as-grown VANs present great promise in terms of structural flexibility and property tunability. Such broad tunability of functionalities is achieved through VAN designs, material selection, growth control, and strain coupling. The as-grown multi-phase VAN films also present enormous advantages, including wafer scale integration, epitaxial quality, sharp atomic interface, as well as designable materials and geometries. This review also covers the research directions with practical device potentials, such as multiplex sensing, high-temperature plasmonics, magneto-optical switching, as well as photonic circuits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-assembled nano- to micron-size fibers from molten R11Ni4In9 intermetallics

A study of the formation of Gd11M4In9 (M = Ni, Pd, Pt) and R11Ni4In9 (R = rare earth) compounds revealed a unique and peculiar property, which is to naturally crystallize in a bundle of self-assembled fibers when cooled from the melt. The fibers, which are nano- to millimeters in cross-section and approximate to 11-40 mm long, grow unidirectionally along a temperature gradient. These compounds adopt the orthorhombic Nd11Pd4In9 structure type (oC48-Cmmm). This structure is layered, with slabs of R atoms alternating with slabs of Ni/In atoms along a short c-axis (much shorter than either the a- or b-axis). The growth direction of the fibers is along the crystallographic c-axis, orthogonal to the a-b plane. Two strong and short In In bonds lie in the a-b plane, which are even shorter than in In metal. Integrated crystal orbital Hamilton population calculations show that the In In bonds create isolated "R8Ni4In9" rods growing along the c-axis, with the In In bonds being part of the rods. This appears to be an important factor explaining the microfibrous nature of these phases. Some physical properties have been measured on the Gd11Ni4In9 homolog. The compound orders ferrimagnetically at T-c approximate to 88 K, and at lower temperatures (46 and 10 K), two other magnetic anomalies were observed, probably due to spin reorientations. As expected from the bonding features, the mechanical, magnetic and electrical properties are strongly anisotropic. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

36 MATERIALS SCIENCE↗

Vertically Aligned Single-Crystalline CoFe 2 O 4 Nanobrush Architectures with High Magnetization and Tailored Magnetic Anisotropy

Micrometer-tall vertically aligned single-crystalline CoFe 2 O 4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Further, magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 μB/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

36 MATERIALS SCIENCE↗

A Conceptual Study for the Autonomous Direct Forming of Lunar Regolith into Flexlock (Trademark) Geomats for Lunar Surface Operations

We describe the conceptual method of an autonomously operable Direct Forming machine that would consume regolith or regolith slag to mold intimately, interlinked elements in a continuous process. The resulting product, one to three meter wide geomats, would be deployed over commonly traversed areas to isolate the astronauts and equipment from underlying dust. The porous geotextile would provide areas for dust settling, thereby mitigating dust impingement on astronaut suits or surface structures. Because of their self-supporting yet flexible structure, these geomats could be assembled into shields and buttresses to protect lunar habitants from radiation, forming a "flexoskeleton" from in situ materials.

Robertson, Luke B.↗

Active Radiative Thermal Switching with Graphene Plasmon Resonators

We theoretically demonstrate a near-field radiative thermal switch based on thermally excited surface plasmons in graphene resonators. The high tunability of graphene enables substantial modulation of near-field radiative heat transfer, which, when combined with the use of resonant structures, overcomes the intrinsically broadband nature of thermal radiation. In canonical geometries, we use nonlinear optimization to show that stacked graphene sheets offer improved heat conductance contrast between “ON” and “OFF” switching states and that a >10× higher modulation is achieved between isolated graphene resonators than for parallel graphene sheets. In all cases, we find that carrier mobility is a crucial parameter for the performance of a radiative thermal switch. Furthermore, we derive shape-agnostic analytical approximations for the resonant heat transfer that provide general scaling laws and allow for direct comparison between different resonator geometries dominated by a single mode. The presented scheme is relevant for active thermal management and energy harvesting as well as probing excited-state dynamics at the nanoscale.

30 DIRECT ENERGY CONVERSION↗

Metastable doubly threaded [3]rotaxanes with a large macrocycle

Ring size is a critically important parameter in many interlocked molecules as it directly impacts many of the unique molecular motions that they exhibit. Reported herein are studies using one of the largest macrocycles reported to date to synthesize doubly threaded [3]rotaxanes. A large ditopic 46 atom macrocycle containing two 2,6-bis(N-alkyl-benzimidazolyl)pyridine ligands has been used to synthesize several metastable doubly threaded [3]rotaxanes in high yield (65–75% isolated) via metal templating. Macrocycle and linear thread components were synthesized and self-assembled upon addition of iron(II) ions to form the doubly threaded pseudo[3]rotaxanes that could be subsequently stoppered using azide–alkyne cycloaddition chemistry. Following demetallation with base, these doubly threaded [3]rotaxanes were fully characterized utilizing a variety of NMR spectroscopy, mass spectrometry, size-exclusion chromatography, and all-atom simulation techniques. Critical to the success of accessing a metastable [3]rotaxane with such a large macrocycle was the nature of the stopper group employed. By varying the size of the stopper group it was possible to access metastable [3]rotaxanes with stabilities in deuterated chloroform ranging from a half-life of <1 minute to ca. 6 months at room temperature potentially opening the door to interlocked materials with controllable degradation rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interface reconstruction with emerging charge ordering in hexagonal manganite

Multiferroic materials, which simultaneously have multiple orderings, hold promise for use in the next generation of memory devices. We report a novel self-assembled MnO double layer forming at the interface between a multiferroic YMnO 3 film and a c-Al 2 O 3 substrate. The crystal structures and the valence states of this MnO double layer were studied by atomically resolved scanning transmission electron microscopy and spectroscopy, as well as density functional theory (DFT) calculations. A new type of charge ordering has been identified within this MnO layer, which also contributes to a polarization along the [001] direction. DFT calculations further establish the occurrence of multiple couplings between charge and lattice in this novel double layer, in addition to the polarization in nearby YMnO 3 single layer. The interface reconstruction reported here creates a new playground for emergent physics, such as giant ferroelectricity and strong magnetoelectric coupling, in manganite systems.

36 MATERIALS SCIENCE↗

Chapter 8: Fluids: liquid crystals—self-assembly of the superlarge and superweak active clothing

At the suggestion of NASA’s Physical Science Research Program in the Space Life and Physical Science Research and Application Division, Paul Chaikin, Noel Clark, and Sidney Nagel organized a focus session and workshop for the 2020 American Physical Society (APS) March meeting under the auspices of the Division of Soft Matter. Three overarching themes emerged from the workshop and are presented with additional details: • Machines made out of machines • Scalable self-sustaining ecosystems • Active materials and metamaterials This report lays out only some of the potential directions for soft matter dynamics over the next two decades. It also lays out the role that gravity plays in the organization of the basic building blocks of matter. Not only will research on soft matter have tremendous application towards understanding its behavior in our terrestrial environment, but also potentially in other NASA programs such as planetary science, exploration, robotics, etc. The attached is a White Paper for the Decadal Survey that consists of an extended Title along with the previous Introduction and Chapter 2.8 from NASA/CP-20205010493.

Soft matter↗

Anisometric C 60 Fullerene Colloids Assisted by Structure-Directing Agent

Colloidal synthesis and assembly provide low cost, large area routes to mesoscale structures. In particular, shape-anisotropic particles may form crystalline, plastic crystalline, complex liquid crystalline and glassy phases. Arrangements in each order class have been used to generate photonic materials. For example, large photonic band gaps have been found for photonic crystals, hyperuniform photonic glasses, and also for plastic crystals at sufficient refractive index contrast. The latter structures support highly isotropic bandgaps that are desirable for free-form waveguides and LED out-coupling. Photonic glasses with optical gain lead to self-tuned lasing by the superposition of multiply scattered light. Typically, extrinsic media such as organic dyes, rare earths, lanthanides and quantum dots are used to impart optical gain in photonic solids. The present work advances fullerene microcrystals as a new materials platform for ‘active’ light emitting in colloid-based photonic crystals. Fullerenes support singlet excited states that recombine to produce a characteristic red photoluminescence. C 60 also has a high refractive index (n ~ 2.2) and transparency (> 560 nm) 9 so that inverse structures are not required.

36 MATERIALS SCIENCE↗

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

Environmental Molecular Sciences Laboratory↗

Investigation of Metal Free Naphthalocyanine Vapor Deposited on Au(111)

Naphthalocyanines (Ncs) are promising candidates for future components in electronic devices and applications. To maximize the efficiency of Nc devices, it is critical to understand their structural and electronic properties and how these are impacted by deposition methods. The formation of a metal free naphthalocyanine (H2Nc) self-assembled monolayer on a Au(111) crystal was investigated by scanning tunneling microscopy under ultra-high-vacuum conditions at room temperature. A rigorous purification and processing procedure was developed to produce high purity, low defect, and well-ordered monolayers. High-resolution STM images reveal epitaxial growth of H2Nc on Au(111) with the observed structure having a molecular spacing of 1.6 ± 0.05 nm, with molecules orientated slightly off (roughly 2.5°) the low density packing direction of Au(111). A commensurate structure having 4 molecules per unit cell and unit cell parameters of A = 3.25 ± 0.05 nm, B = 3.17 ± 0.05 nm, and α = 87.5 ± 2° is proposed. Orbital-mediated tunneling spectroscopy was used to examine the electronic properties of individual molecules within the thin film. The first ionization potential and electron affinity of H2Nc adsorbed on Au(111) were measured to be -0.68 ± 0.03 and 1.12 ± 0.02 eV, relative to the Fermi energy.

Environmental Molecular Sciences Laboratory↗