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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 505 records · Page 28

Optical anisotropy of GaSb type-II nanorods on vicinal (111)B GaAs

We form self-assembled GaSb type-II nanorods on a vicinal (111)B GaAs substrate by molecular beam epitaxy and study their optical anisotropy. The GaSb nanorods are elongated and aligned along the [-1 0 1] direction, where the average length, width, and height are about 84, 30, and 2.5 nm. In polarized photoluminescence (PL) measurements, the peak of the GaSb nanorods is observed at about 1.1 eV, where the PL intensity is largest for the [-1 0 1] polarization and smallest for the polarization perpendicular to it. The degree of polarization is more than 20% and depends on the recombination energy. By comparing with a theoretical model based on 4 x 4 Luttinger-Kohn Hamiltonian, we find that the experimental results are explained by considering the Sb/As inter-diffusion and the nanorod height distribution.

36 MATERIALS SCIENCE↗

Bioorganic nanodots for non-volatile memory devices

In recent years we are witnessing an intensive integration of bio-organic nanomaterials in electronic devices. Here we show that the diphenylalanine bio-molecule can self-assemble into tiny peptide nanodots (PNDs) of ∼2 nm size, and can be embedded into metal-oxide-semiconductor devices as charge storage nanounits in non-volatile memory. For that purpose, we first directly observe the crystallinity of a single PND by electron microscopy. We use these nanocrystalline PNDs units for the formation of a dense monolayer on SiO{sub 2} surface, and study the electron/hole trapping mechanisms and charge retention ability of the monolayer, followed by fabrication of PND-based memory cell device.

36 MATERIALS SCIENCE↗

Kinetic preference for the 3'-5'-linked dimer in the reaction of guanosine 5'-phosphorylmorpholinamide with deoxyguanosine 5'-phosphoryl-2-methylimidazolide as a function of poly(C) concentration

The formation of the internucleotide bond in diguanylate synthesis was studied in aqueous solution at pH 8 and 0.2 M Mg2+ in the presence and absence of polycytidylate, poly(C). The investigation was simplified by using guanosine 5'-phosphorylmorpholinamide, mor-pG, which can act only as a nucleophile, and deoxyguanosine 5'-phosphoryl-2-methylimidazolide, 2-MeImpdG, which can act only as an electrophile. The time-dependent product distribution was monitored by high-performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS). In the absence of poly(C) the reaction between mor-pG and 2-MeImpdG yielded small amounts of the dimer mor-pGpdG with a regioselectivity of 2'-5':3'-5' = 3.5. In the presence of poly(C) dimer yields increased and a reversal in regioselectivity occurred; both effects were in proportion to the concentration of the polymer. The results can be quantitatively explained with the proposition that poly(C), acting as the template, catalyzes the reaction between template-bound monomers by about a factor of 4-5 over the reaction in solution and yields dimers with a regioselectivity of 2'-5':3'-5' approximately 0.33. These findings illustrate the intrinsic preference of guanosine monomers to correctly self-assemble on the appropriate template.

NASA Discipline Exobiology↗

Sculpting the Plasmonic Responses of Nanoparticles by Directed Electron Beam Irradiation

Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into associated mechanisms. However, modern synthesis processes for plasmonic nanostructures are often limited in the types of accessible geometry, and materials and are limited to spatial precisions on the order of tens of nm, precluding the direct exploration of critical aspects of the structure-property relationships. Here, the atomic-sized probe of the scanning transmission electron microscope is used to perform precise sculpting and design nanoparticle configurations. Using low-loss EELS, dynamic analyses of the evolution of the plasmonic response are provided. It is shown that within self-assembled systems of nanoparticles, individual nanoparticles can be selectively removed, reshaped, or patterned with nanometer-level resolution, effectively modifying the plasmonic response in both space and energy. This process significantly increases the scope for design possibilities and presents opportunities for unique structure development, which are ultimately the key for nanophotonic design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Directed Pore Uptake and Phase Separation of Surfactant Solutions under Confinement

The ability of a porous material to uptake and release molecules is determined by the thermodynamic state of preadsorbed surfactants in pore space. Yet, the effect of spatial confinement on the thermodynamic state of the surfactants is poorly understood. In this study, we use a combination of small-angle neutron scattering experiments and all-atom molecular dynamics simulations to develop a better understanding of the effect of confinement on self-assembly and temperature-induced liquid–liquid phase separation of surfactant solutions. Here, we study the demixing of a model nonionic surfactant triethyleneglycol monohexyl ether (C 6 E 3 ) in tubular nanopores of the SBA-15 silica material (pore diameter of 8.6 nm). We find that the nonionic surfactants display an enhanced in situ aggregation behavior in silica pores upon increasing the temperature above the lower critical solution temperature (LCST). The surfactant molecules directly bound to the pore walls act as anchor sites for subsequent adsorption, resulting in the increased uptake of nonanchored surfactants upon increasing temperature and driving an increase in the size of assemblies. The nonanchored surfactant molecules can be released into a bulk solvent by decreasing the temperature below LCST. This ability of C 6 E 3 surfactant allows reversible partitioning of secondary molecules (here dye) dissolved in the cores of surfactant micelles between the pore space and bulk solvent. The findings presented in the article provide fundamental insights into the surfactant assembly in confinement, which is crucial in the development of new multiresponsive materials for isolating and recovering molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diverse Bilayer Morphologies Achieved via α-Helix-to-β-Sheet Transitions in a Short Amphiphilic Peptide

Transmembrane proteins are functional macromolecules that direct the flow of small molecules and ions across a lipid bilayer. Here, we propose the development of helical peptide amphiphiles that will serve as both the bilayer and the functional unit of a self-assembled peptide bilayer membrane. The peptide, K 3 L 12 , was designed not only to possess dimensions similar to that of a lipid bilayer but also to yield a structurally robust, alpha-helical bilayer. The formation of alpha-helices is pH-dependent, and upon annealing the sample, a transition from alpha-helices to $\beta$-sheets can be controlled, as indicated by optical and vibrational spectroscopies. Imaging the materials confirms morphologies similar to that of a lipid bilayer but rich in $\alpha$-helices. Annealing the samples yields a shift in the morphology from bilayers to curled disks, fibers, and sheets. The structural robustness of the material can facilitate the incorporation of many functions into the bilayer assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Room Temperature Lasing from Semiconducting Single-Walled Carbon Nanotubes

Miniaturized near-infrared semiconductor lasers that are able to generate coherent light with low energy consumption have widespread applications in fields such as optical interconnects, neuromorphic computing, and deep-tissue optogenetics. With optical transitions at near-infrared wavelengths, diameter-tunable electronic structures, and superlative optoelectronic properties, semiconducting single-walled carbon nanotubes (SWCNTs) are promising candidates for nanolaser applications. However, despite significant efforts in this direction and recent progress toward enhancing spontaneous emission from SWCNTs through Purcell effects, SWCNT-based excitonic lasers have not yet been demonstrated. Leveraging an optimized cavity-emitter integration scheme enabled by a self-assembly process, here we couple SWCNT emission to the whispering gallery modes supported by polymer microspheres, resulting in room temperature excitonic lasing with an average lasing threshold of 4.5 kW/cm 2 . The high photostability of SWCNTs allows stable lasing for prolonged duration with minimal degradation. Finally, this experimental realization of excitonic lasing from SWCNTs, combined with their versatile electronic and optical properties that can be further controlled by chemical modification, offers far-reaching opportunities for tunable near-infrared nanolasers that are applicable for optical signal processing, in vivo biosensing, and optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain-induced self-assembly of Ge nanodashes, nanodumbbells, and dot chains on Si(001)

We investigate the growth of self-assembled Ge nanostructures on top of embedded Ge nanowires on Si(001) substrates. Ge nanostructures, such as nanodashes, nanodumbbells, and dot chains are observed simply by tuning the growth temperature and thickness of the Si spacer between the Ge layers. The self-assembly process is governed by the surface strain fields generated by the embedded Ge nanowires and is well-described by our theoretical calculations. The catalyst-free and horizontal growth of such Ge nanostructures directly on Si(001) is attractive for investigating exotic transport properties through Si/Ge-based quantum devices.

36 MATERIALS SCIENCE↗

Mechanisms underlying the active self-assembly of microtubule rings and spools

Here, active self-assembly offers a powerful route for the creation of dynamic multiscale structures that are presently inaccessible with standard microfabrication techniques. One such system uses the translation of microtubule filaments by surface-tethered kinesin to actively assemble nanocomposites with bundle, ring, and spool morphologies. Attempts to observe mechanisms involved in this active assembly system have been hampered by experimental difficulties with performing observation during buffer exchange and photodamage from fluorescent excitation. In the present work, we used a custom microfluidic device to remove these limitations and directly study ring/spool formation, including the earliest events (nucleation) that drive subsequent nanocomposite assembly. Three distinct formation events were observed: pinning, collisions, and induced curvature. Of these three, collisions accounted for the majority of event leading to ring/spool formation, while the rate of pinning was shown to be dependent on the amount of photodamage in the system. We further showed that formation mechanism directly affects the diameter and rotation direction of the resultant rings and spools. Overall, the fundamental understanding described in this work provides a foundation by which the properties of motor-driven, actively assembled nanocomposites may be tailored toward specific applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

PCM1 coordinates centrosome asymmetry with polarized endosome dynamics to regulate daughter cell fate

Vertebrate radial glia progenitors (RGPs) balance self-renewal and differentiation through asymmetric cell division (ACD), which involves unequal centrosome inheritance. How centrosome asymmetry directs cell fate remains poorly understood. Here, we identify Pericentriolar material 1 (Pcm1) as a key player in this process. In zebrafish embryonic RGPs, Pcm1 is asymmetrically associated with Cep83, a mother centrosome marker. Using in vivo time-lapse imaging and nanoscale-resolution expansion microscopy, we detect Pcm1 on Notch ligand-containing endosomes, where it interacts–either directly or indirectly–with Par-3 and dynein. Loss of pcm1 disrupts endosome dynamics, increasing neuronal differentiation at the expense of RGP self-renewal. Mechanistically, Pcm1 facilitates the transition from Rab5b to Rab11a and promotes the assembly of Par-3 and dynein macromolecular complexes on recycling endosomes. Furthermore, we find conserved PARD3-PCM1-CEP83-RAB11 associations in human cortical brain organoids. Our findings uncover that Pcm1 links centrosome asymmetry to polarized endosome trafficking, thereby regulating RGP fate decisions.

Cell fate and cell lineage↗

Communication: Programmable self-assembly of thin-shell mesostructures

For this article, we study numerically the possibility of programmable self-assembly of various thin-shell architectures. They include clusters isomorphic to fullerenes C 20 and C 60 , finite and infinite sheets, tube-shaped and toroidal mesostructures. Our approach is based on the recently introduced directionally functionalized nanoparticle platform, for which we employ a hybrid technique of Brownian dynamics with stochastic bond formation. By combining a number of strategies, we were able to achieve a near-perfect yield of the desired structures with a reduced “alphabet” of building blocks. Among those strategies are the following: the use of bending rigidity of the interparticle bond as a control parameter, programming the morphology with a seed architecture, use of chirality-preserving symmetries for reduction of the particle alphabet, and the hierarchic approach.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Rapid Polymer Sequencer

Method and system for rapid and accurate determination of each of a sequence of unknown polymer components, such as nucleic acid components. A self-assembling monolayer of a selected substance is optionally provided on an interior surface of a pipette tip, and the interior surface is immersed in a selected liquid. A selected electrical field is impressed in a longitudinal direction, or in a transverse direction, in the tip region, a polymer sequence is passed through the tip region, and a change in an electrical current signal is measured as each polymer component passes through the tip region. Each of the measured changes in electrical current signals is compared with a database of reference electrical change signals, with each reference signal corresponding to an identified polymer component, to identify the unknown polymer component with a reference polymer component. The nanopore preferably has a pore inner diameter of no more than about 40 nm and is prepared by heating and pulling a very small section of a glass tubing.

Stolc, Viktor↗

Tuning the optical emission of MoS{sub 2} nanosheets using proximal photoswitchable azobenzene molecules

We report photoluminescence measurements performed on monolayer- and two-layer-MoS{sub 2} placed on two types of mixed self-assembled monolayers (mSAMs) of photoswitchable azobenzene molecules. The two mSAMs differ via the electronegative character of the azobenzene derivatives. Thin layers of a transition metal dichalcogenide—MoS{sub 2}—were mechanically exfoliated on mSAM to allow for direct interaction between the molecules and the MoS{sub 2} layers. When the MoS{sub 2} nanosheet is in contact with the electropositive azobenzene molecules in trans configuration, an emission side band at lower energies and at low excitation powers suggest n-type doping. The photoisomerization of the molecules from trans to cis configuration lowers the doping, quenching the side band and enhancing the overall PL efficiency by a factor of ∼3. Opposite results were observed with the chlorinated, more electronegative molecules, exhibiting a reversed trend in the PL efficiency between trans and cis, but with an overall larger intensity. The type of doping induced by the two types of mSAMs was determined by Kelvin probe force microscopy technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Temperature-Dependent Sheet and Contact Resistivity Measurements on Ag and Ag-Ni Circuit Pastes

The metal circuits and brazes used in electronic, energy conversion, and/or energy storage devices often have difficulty wetting and adhering to ceramic and/or ceramic-passivated metal substrates. Here, a novel Particle Interlayer Directed Wetting and Spreading (PIDWAS) technique is demonstrated that utilizes screen printing, the low wetting angle of silver on nickel, and the high work of adhesion between nickel and various ceramics to produce well-adhered, self-assembled silver patterns on ceramic and/or stainless-steel substrates not normally wet by silver. The resulting Ag-Ni circuits have higher sapphire adhesion strengths (up to 30 MPa on sapphire), higher densities (>97% on sapphire), and similar high-temperature electronic resistivities to those made using commercially-available Heraeus C8710 or DAD-87 silver circuit pastes. Similarly, Ag-Ni brazes between a variety of ceramic and/or stainless-steel substrates have better microstructural stability with rapid thermal cycling, reduction-oxidation cycling, and dual atmosphere isothermal aging than conventional Ag-CuO brazes. In addition, the residual Ni in these Ag-Ni circuits and brazes can be used to chemically getter surface segregated Al, ensuring low contact resistances on a variety of chromia- and/or alumina-passivated stainless steels. Reference: [1] Hu G, Zhou Q, Bhatlawande A, Park J, Termuhlen R, Ma Y, Bieler TR, Yu HC, Qi Y, Hogan T & Nicholas JD. Patterned Nickel Interlayers for Enhanced Silver Wetting, Spreading and Adhesion on Ceramic Substrates. Scripta Materialia, 2021; 196, 113767. 10.1016/j.scriptamat.2021.113767 [2] Park J, Phongpreecha T, Nicholas JD & Qi Y. Enhanced Liquid Metal Wetting on Oxide Surfaces via Patterned Particles. Acta Materialia, 2020; 199, 551-560. 10.1016/j.actamat.2020.08.037

Bhatlawande, Aishwarya↗

Scalable assembly of patterned ordered functional micelle arrays: final LDRD report

In this project, we demonstrated the synthesis of polystyrene-polyvinylpyridyne (PS-PVP) micelles, functionalization of these micelles to form organic/inorganic composite nanoparticles, and template directed assembly of dynamic PS-PVP micelles into features defined via soft nanoimprint lithography. We demonstrated unique assembly properties of dynamic micellar nanoparticles by combining a top down lithographic nanopatterning technique with a solution based bottom up self-assembly.

Fan, Hongyou↗

Metal-Templated Design of Chemically Switchable Protein Assemblies with High-Affinity Coordination Sites

To mimic a hypothetical pathway for protein evolution, we previously tailored a monomeric protein (cyt cb562) for metal-mediated self-assembly, followed by re-design of the resulting oligomers for enhanced stability and metal-based functions. We show that a single hydrophobic mutation on the cyt cb562 surface drastically alters the outcome of metal-directed oligomerization to yield a new trimeric architecture, (TriCyt1)3. This nascent trimer was redesigned into second and third-generation variants (TriCyt2)3 and (TriCyt3)3 with increased structural stability and preorganization for metal coordination. The three TriCyt variants combined furnish a unique platform to 1) provide tunable coupling between protein quaternary structure and metal coordination, 2) enable the construction of metal/pH-switchable protein oligomerization motifs, and 3) generate a robust metal coordination site that can coordinate all mid-to-late first-row transition-metal ions with high affinity.

Albert Kakkis↗

Hierarchically ordered porous transition metal compounds from one-pot type 3D printing approaches

Solution-based soft matter self-assembly (SA) promises unique material structures and properties from approaches including additive manufacturing/three-dimensional (3D) printing. The 3D printing of periodically ordered porous functional inorganic materials through SA unfolding during printing remains a major challenge, however, due to the often vastly different ordering kinetics of separate processes at different length scales. Here, we report a “one-pot” direct ink writing process to produce hierarchically porous transition metal nitrides and precursor oxides from block copolymer (BCP) SA. Heat treatment protocols identified in various environments enable mesostructure retention in the final crystalline materials with periodic lattices on three distinct length scales. Moreover, embedded printing enables the first BCP directed mesoporous non-self-supporting helical oxides and nitrides. Resulting nitrides are superconducting, with record nanoconfinement-induced upper critical fields correlated with BCP molar mass and record surface areas for compound superconductors. Results suggest scalable porous functional inorganic material formation approaches for applications including catalysis, sensing, and microelectronics.

36 MATERIALS SCIENCE↗