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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 451 records · Page 25

Test bed concentrator mirrors

The test bed concentrator (TBC) was des point focusing distributed receiver (PFDR) systems. The reflective surface of the concentrator was fabricated using mirror facet designs and techniques. The facets are made by bonding mirrored glass to spherically-conducted substrates. Several aspects of earlier work were reevaluated for application to the TBC: optimum glass block size, material selection, environmental test, optical characteristics, and reliability. A detailed explanation of tooling, substrate preparation, testing techniques, and mirror assembly is presented.

Argoud, M. J.↗

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction↗

Radiative Performance of Rare Earth Garnet Thin Film Selective Emitters

In this paper we present the first emitter efficiency results for the thin film 40 percent Er-1.5 percent Ho YAG (Yttrium Aluminum Garnet, Y3Al5O12) and 25 percent Ho YAG selective emitter at 1500 K with a platinum substrate. Spectral emittance and emissive power measurements were made (1.2 less than lambda less than 3.2 microns). Emitter efficiency and power density are significantly improved with the addition of multiple rare earth dopants. Predicted efficiency results are presented for an optimized (equal power density in the Er, (4)I(sub 15/2)-(4)I(sub 13/2) at 1.5 microns, and Ho, (5)I(sub 7)-(5)I(sub 8) at 2.0 micron emission bands) Er-Ho YAG thin film selective emitter.

Lowe, Roland A.↗

Structural basis of colibactin activation by the ClbP peptidase

Abstract Colibactin, a DNA cross-linking agent produced by gut bacteria, is implicated in colorectal cancer. Its biosynthesis uses a prodrug resistance mechanism: a non-toxic precursor assembled in the cytoplasm is activated after export to the periplasm. This activation is mediated by ClbP, an inner-membrane peptidase with an N-terminal periplasmic catalytic domain and a C-terminal three-helix transmembrane domain. Although the transmembrane domain is required for colibactin activation, its role in catalysis is unclear. Our structure of full-length ClbP bound to a product analog reveals an interdomain interface important for substrate binding and enzyme stability and interactions that explain the selectivity of ClbP for the N -acyl- d -asparagine prodrug motif. Based on structural and biochemical evidence, we propose that ClbP dimerizes to form an extended substrate-binding site that can accommodate a pseudodimeric precolibactin with its two terminal prodrug motifs in the two ClbP active sites, thus enabling the coordinated activation of both electrophilic warheads.

Biochemistry & Molecular Biology↗

Enzymatic Laser-Induced Graphene Biosensor for Electrochemical Sensing of the Herbicide Glyphosate

Glyphosate is a globally applied herbicide yet it has been relatively undetectable in-field samples outside of gold-standard techniques. Its presumed nontoxicity toward humans has been contested by the International Agency for Research on Cancer, while it has been detected in farmers’ urine, surface waters and crop residues. Rapid, on-site detection of glyphosate is hindered by lack of field-deployable and easy-to-use sensors that circumvent sample transportation to limited laboratories that possess the equipment needed for detection. Herein, the flavoenzyme, glycine oxidase, immobilized on platinum-decorated laser-induced graphene (LIG) is used for selective detection of glyphosate as it is a substrate for GlyOx. The LIG platform provides a scaffold for enzyme attachment while maintaining the electronic and surface properties of graphene. The sensor exhibits a linear range of 10–260 µm, detection limit of 3.03 µm, and sensitivity of 0.991 nA µm -1 . The sensor shows minimal interference from the commonly used herbicides and insecticides: atrazine, 2,4-dichlorophenoxyacetic acid, dicamba, parathion-methyl, paraoxon-methyl, malathion, chlorpyrifos, thiamethoxam, clothianidin, and imidacloprid. Sensor function is further tested in complex river water and crop residue fluids, which validate this platform as a scalable, direct-write, and selective method of glyphosate detection for herbicide mapping and food analysis.

47 OTHER INSTRUMENTATION↗

Atomic-Force Microscopy Probe-Activated Morphological Transformations in a Nanophase Copper Wetting Layer on Silicon

The phase transition of the nanophase Cu{sub 2}Si wetting layer on a Si(001) substrate to more stable Cu silicide has been selectively activated by atomic-force microscopy in air. The transition is accompanied by an increase in the lateral size and height of grains and a decrease in their density. The effect that has been identified can be used to form ordered nanoisland ensembles and in nanolithography.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Characterization of Heteroepitaxial GaAs Films Grown on Si Using Selective Area Nucleation

Selective area growth of GaAs on patterned Si substrates is a potentially low-cost approach to integrate III-V and Si materials for multijunction solar cells. The use of nanoscale openings in a dielectric material can minimize nucleation-related defects and allow thinner buffer layers to be used to accommodate strain and trap defects caused by lattice mismatch between Si and epitaxial III-V layers. We have developed a process to grow coalesced GaAs thin films on Si substrates using buffer layers patterned by soft nanoimprint lithography (SNIL). We use photoelectrochemistry to probe the performance of these films as photovoltaic absorbers, and discuss techniques to improve the material quality of the GaAs epilayer.

14 SOLAR ENERGY↗

Structure and energetics of pairwise interactions between proteasome subunits RPN2, RPN13, and ubiquitin clarify a substrate recruitment mechanism

This work presents that the 26S proteasome is a large cellular assembly that mediates the selective degradation of proteins in the nucleus and cytosol and is an established target for anticancer therapeutics. Protein substrates are typically targeted to the proteasome through modification with a polyubiquitin chain, which can be recognized by several proteasome-associated ubiquitin receptors. One of these receptors, RPN13/ADRM1, is recruited to the proteasome through direct interaction with the large scaffolding protein RPN2 within the 19S regulatory particle. To better understand the interactions between RPN13, RPN2, and ubiquitin, we used human proteins to map the RPN13-binding epitope to the C-terminal 14 residues of RPN2, which, like ubiquitin, binds the N-terminal pleckstrin-like receptor of ubiquitin (PRU) domain of RPN13. We also report the crystal structures of the RPN13 PRU domain in complex with peptides corresponding to the RPN2 C terminus and ubiquitin. Through mutational analysis, we validated the RPN2-binding interface revealed by our structures and quantified binding interactions with surface plasmon resonance and fluorescence polarization. In contrast to a previous report, we find that RPN13 binds ubiquitin with an affinity similar to that of other proteasome-associated ubiquitin receptors and that RPN2, ubiquitin, and the deubiquitylase UCH37 bind to RPN13 with independent energetics. In conclusion, these findings provide a detailed characterization of interactions that are important for proteasome function, indicate ubiquitin affinities that are consistent with the role of RPN13 as a proteasomal ubiquitin receptor, and have major implications for the development of novel anticancer therapeutics.

59 BASIC BIOLOGICAL SCIENCES↗

Chip packaging technique

A hermetically sealed package for at least one semiconductor chip is provided which is formed of a substrate having electrical interconnects thereon to which the semiconductor chips are selectively bonded, and a lid which preferably functions as a heat sink, with a hermetic seal being formed around the chips between the substrate and the heat sink. The substrate is either formed of or includes a layer of a thermoplastic material having low moisture permeability which material is preferably a liquid crystal polymer (LCP) and is a multiaxially oriented LCP material for preferred embodiments. Where the lid is a heat sink, the heat sink is formed of a material having high thermal conductivity and preferably a coefficient of thermal expansion which substantially matches that of the chip. A hermetic bond is formed between the side of each chip opposite that connected to the substrate and the heat sink. The thermal bond between the substrate and the lid/heat sink may be a pinched seal or may be provided, for example by an LCP frame which is hermetically bonded or sealed on one side to the substrate and on the other side to the lid/heat sink. The chips may operate in the RF or microwave bands with suitable interconnects on the substrate and the chips may also include optical components with optical fibers being sealed into the substrate and aligned with corresponding optical components to transmit light in at least one direction. A plurality of packages may be physically and electrically connected together in a stack to form a 3D array.

Jayaraj, Kumaraswamy↗

Spectroelectrochemical investigations of nickel cyclam indicate different reaction mechanisms for electrocatalytic CO 2 and H + reduction

Rising levels of atmospheric carbon dioxide continue to motivate the development of catalysts that can efficiently convert CO 2 to useful products in water without substantial amounts of H 2 formed as a byproduct. In addition to synthetic efforts, mechanistic investigations on existing catalysts are necessary to understand the molecular factors contributing to activity and selectivity, which can guide rational improvements and increase catalyst robustness. [Ni(cyclam)] 2+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) is one such catalyst, known for decades to be capable of selective CO 2 reduction to CO in water, but with little mechanistic information experimentally established or catalytic intermediates characterized. To better understand the mechanisms of aqueous H + and CO 2 reduction by [Ni(cyclam)] 2+ , spectroelectrochemical investigations were performed in conjunction with activity assays. Both large surface area glassy carbon and amorphous graphite rod working electrodes were tested, with the latter found to be significantly more active and selective for CO production. Optical, resonance Raman, and EPR spectroelectrochemical experiments on [Ni(cyclam)] 2+ during catalysis under N 2 , CO 2 , and CO gases show the appearance of a single species, independent of electrode used. Identical signals are observed under oxidizing potentials. Spectroscopic and electrochemical analysis coupled with density functional theory calculations suggest that the signals observed originate from [Ni(cyclam)(H 2 PO4)] 2+ . The generation of a NiIII species under catalytic, reducing conditions suggests an ECCE mechanism for H + reduction by [Ni(cyclam)] 2+ , which differs from the proton-coupled, ECEC pathway proposed for CO 2 reduction. The divergent mechanisms seen for the two reactions may underlie the differential reactivity of [Ni(cyclam)] 2+ towards each substrate, with implications for the design of increasingly selective molecular catalysts. Finally, this observation also highlights the substantial impact of buffer and electrode choice when characterizing and benchmarking the catalytic properties of new compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technology development of fabrication techniques for advanced solar dynamic concentrators

The objective of the advanced concentrator program is to develop the technology that will lead to lightweight, highly reflective, accurate, scaleable, and long lived space solar dynamic concentrators. The advanced concentrator program encompasses new and innovative concepts, fabrication techniques, materials selection, and simulated space environmental testing. Fabrication techniques include methods of fabricating the substrates and coating substrate surfaces to produce high quality optical surfaces, acceptable for further coating with vapor deposited optical films. The selected materials to obtain a high quality optical surface include microsheet glass and Eccocoat EP-3 epoxy, with DC-93-500 selected as a candidate silicone adhesive and levelizing layer. The following procedures are defined: cutting, cleaning, forming, and bonding microsheet glass. Procedures are also defined for surface cleaning, and EP-3 epoxy application. The results and analyses from atomic oxygen and thermal cycling tests are used to determine the effects of orbital conditions in a space environment.

Richter, Scott W.↗

Direct observation of chirality-induced spin selectivity in electron donor–acceptor molecules

The role of chirality in determining the spin dynamics of photoinduced electron transfer in donor-acceptor molecules remains an open question. Although chirality-induced spin selectivity (CISS) has been demonstrated in molecules bound to substrates, experimental information about whether this process influences spin dynamics in the molecules themselves is lacking. Here we used time-resolved electron paramagnetic resonance spectroscopy to show that CISS strongly influences the spin dynamics of isolated covalent donor–chiral bridge–acceptor (D-Bχ-A) molecules in which selective photoexcitation of D is followed by two rapid, sequential electron-transfer events to yield D •+ -Bχ-A •– . Exploiting this phenomenon affords the possibility of using chiral molecular building blocks to control electron spin states in quantum information applications.

Science & Technology - Other Topics↗

Selective-area growth of heavily n–doped GaAs nanostubs on Si(001) by molecular beam epitaxy

Using an aspect ratio trapping technique, we demonstrate molecular beam epitaxy of GaAs nanostubs on Si(001) substrates. Nanoholes in a SiO{sub 2} mask act as a template for GaAs-on-Si selective-area growth (SAG) of nanostubs 120 nm tall and ≤100 nm in diameter. We investigate the influence of growth parameters including substrate temperature and growth rate on SAG. Optimizing these parameters results in complete selectivity with GaAs growth only on the exposed Si(001). Due to the confined-geometry, strain and defects in the GaAs nanostubs are restricted in lateral dimensions, and surface energy is further minimized. We assess the electrical properties of the selectively grown GaAs nanostubs by fabricating heterogeneous p{sup +}–Si/n{sup +}–GaAs p–n diodes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Enhanced degradation of aluminum metal in the presence of selected microorganisms

Experiments were conducted to determine the effects of microorganisms, substrates, pressures, humidities, and oxygen concentrations upon aluminum corrosion. In addition, the effects of microbes upon coated and treated aluminum were examined and an attempt to correlate aluminum in solution with degradation of the samples was undertaken. The organisms, humidities, oxygen levels, and substrates all played a major role in the corrosion of aluminum. Quantitation of aluminum losses indicated that the total metal losses from inoculated samples were significantly greater than those of the uninoculated samples.

Tennyson, J. M.↗

Technology development of fabrication techniques for advanced solar dynamic concentrators

The objective of the advanced concentrator program is to develop the technology that will lead to lightweight, highly reflective, accurate, scaleable, and long lived space solar dynamic concentrators. The advanced concentrator program encompasses new and innovative concepts, fabrication techniques, materials selection, and simulated space environmental testing. Fabrication techniques include methods of fabricating the substrates and coating substrate surfaces to produce high-quality optical surfaces, acceptable for further coating with vapor deposited optical films. The selected materials to obtain a high quality optical surface include microsheet glass and Eccocoat EP-3 epoxy, with DC-93-500 selected as a candidate silicone adhesive and levelizing layer. The following procedures are defined: cutting, cleaning, forming, and bonding microsheet glass. Procedures are also defined for surface cleaning, and EP-3 epoxy application. The results and analyses from atomic oxygen and thermal cycling tests are used to determine the effects of orbital conditions in a space environment.

Richter, Scott W.↗

The Effect of Temperature on the Radiative Performance of Ho-Yag Thin Film Selective Emitters

We present the emitter efficiency results for the thin film 25 percent Ho YAG (Yttrium Aluminum Garnet, Y3Al5O12) selective emitter from 1000 to 1700 K with a platinum substrate. Spectral emittance and emissive power measurements were made (1.2 less than lambda less than 3.2 microns) and used to calculate the radiative efficiency. The radiative efficiency and power density of rare earth doped selective emitters are strongly dependent on temperature and experimental results indicate an optimum temperature (1650 K for Ho YAG) for thermophotovoltaic (TPV) applications.

Lowe, Roland A.↗

Digital Maskless Photolithographic Patterning of DNA-Functionalized Poly(ethylene glycol) Diacrylate Hydrogels with Visible Light Enabling Photodirected Release of Oligonucleotides

Soft biomaterials possessing structural hierarchy have growing applications in lab-on-chip devices, artificial tissues, and micromechanical and chemomechanical systems. The ability to integrate sets of biomolecules, specifically DNA, within hydrogel substrates at precise locations could offer the potential to form and modulate complex biochemical processes with DNA-based molecular switches in such materials and provide a means of creating dynamic spatial patterns, thus enabling spatiotemporal control of a wide array of reaction-diffusion phenomena prevalent in biological systems. In this paper, we develop a means of photopatterning two-dimensional DNA-functionalized poly(ethylene glycol) diacrylate (PEGDA) hydrogel architectures with an aim toward these applications. While PEGDA photopatterning methods are well-established for the fabrication of hydrogels, including those containing oligonucleotides, the photoinitiators typically used have significant crosstalk with many UV-photoswitchable chemistries including nitrobenzyl derivatives. We demonstrate the digital photopatterning of PEGDA-co-DNA hydrogels using a blue light-absorbing (470 nm peak) photoinitiator system and macromer comprised of camphorquinone, triethanolamine, and poly(ethylene glycol) diacrylate ($M$ n = 575) that minimizes absorption in the UV-A wavelength range commonly used to trigger photoswitchable chemistries. We demonstrate this method using digital maskless photolithography within microfluidic devices that allows for the reliable construction of multidomain structures. The method achieves feature resolutions as small as 25 μm, and the resulting materials allow for lateral isotropic bulk diffusion of short single-stranded (ss) DNA oligonucleotides. Finally, we show how the use of these photoinitiators allows for orthogonal control of photopolymerization and UV-photoscission of acrylate-modified DNA containing a 1-(2-nitrophenyl) ethyl spacer to selectively cleave DNA from regions of a PEGDA substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗