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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS2009

Understanding the Activation and Solution Properties of Lunar Dust for Future Lunar Habitation

The decision to return humans to the moon by 2020 makes it imperative to understand the effects of lunar dust on human and mechanical systems.( Bush 2004; Gaier 2005; Mendell 2005) During the Apollo missions, dust was found to cause numerous problems for various instruments and systems. Additionally, the dust may have caused health issues for some of the astronauts.(Gaier 2005; Rowe 2007) It is necessary, therefore, for studies to be carried out in a variety of disciplines in order to mitigate the effects of the dust as completely as possible. Due to the lack of an atmosphere, there is nothing to protect the lunar soil from ultraviolet radiation, solar wind, and meteorite impacts. These processes could all serve to "activate" the soil, or produce reactive surface species. In order to understand the possible toxic effects of the reactive dust, it is necessary to "reactivate" the dust, as samples returned during the Apollo missions were exposed to the atmosphere of the Earth. We have used grinding and exposure to UV radiation in order to mimic some of the processes occurring on the lunar surface. To monitor the reactivity of the dust, we have measured the ability of the dust to produce hydroxyl radicals in solution. These radicals have been measured using a novel fluorescent technique developed in our laboratory,(Wallace et al. 2008) as well as using electron paramagnetic resonance (EPR).

Wallace, William T.↗
NASA NTRS2010

NASA Tech Briefs, January 2010

Topics covered include: Cryogenic Flow Sensor; Multi-Sensor Mud Detection; Gas Flow Detection System; Mapping Capacitive Coupling Among Pixels in a Sensor Array; Fiber-Based Laser Transmitter for Oxygen A-Band Spectroscopy and Remote Sensing; Low-Profile, Dual-Wavelength, Dual-Polarized Antenna; Time-Separating Heating and Sensor Functions of Thermistors in Precision Thermal Control Applications; Cellular Reflectarray Antenna; A One-Dimensional Synthetic-Aperture Microwave Radiometer; Electrical Switching of Perovskite Thin-Film Resistors; Two-Dimensional Synthetic-Aperture Radiometer; Ethernet-Enabled Power and Communication Module for Embedded Processors; Electrically Variable Resistive Memory Devices; Improved Attachment in a Hybrid Inflatable Pressure Vessel; Electrostatic Separator for Beneficiation of Lunar Soil; Amorphous Rover; Space-Frame Antenna; Gear-Driven Turnbuckle Actuator; In-Situ Focusing Inside a Thermal Vacuum Chamber; Space-Frame Lunar Lander; Wider-Opening Dewar Flasks for Cryogenic Storage; Silicon Oxycarbide Aerogels for High-Temperature Thermal Insulation; Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C; Designs and Materials for Better Coronagraph Occulting Masks; Fuel-Cell-Powered Vehicle with Hybrid Power Management; Fine-Water-Mist Multiple-Orientation-Discharge Fire Extinguisher; Fuel-Cell Water Separator; Turbulence and the Stabilization Principle; Improved Cloud Condensation Nucleus Spectrometer; Better Modeling of Electrostatic Discharge in an Insulator; Sub-Aperture Interferometers; Terahertz Mapping of Microstructure and Thickness Variations; Multiparallel Three-Dimensional Optical Microscopy; Stabilization of Phase of a Sinusoidal Signal Transmitted Over Optical Fiber; Vacuum-Compatible Wideband White Light and Laser Combiner Source System; Optical Tapers as White-Light WGM Resonators; EPR Imaging at a Few Megahertz Using SQUID Detectors; Reducing Field Distortion in Magnetic Resonance Imaging; Fluorogenic Cell-Based Biosensors for Monitoring Microbes; A Constant-Force Resistive Exercise Unit; GUI to Facilitate Research on Biological Damage from Radiation; On-Demand Urine Analyzer; More-Realistic Digital Modeling of a Human Body; and Advanced Liquid-Cooling Garment Using Highly Thermally Conductive Sheets.

Source record↗
NASA NTRS2010

Understanding the Reactivity of Lunar Dust for Future Lunar Missions

Fluorescence and EPR can be used to measure the reactivity of lunar soil. Lunar soil is highly activated by grinding. Reactivity is dependent upon soil maturity and locale. Maturity is based on the amount of nanophase iron (np-Fe) in a soil relative to the total iron (FeO). Lunar soil activity ia a direct function of the amount of np-Fe present. Reactive soil can be "deactivated" by humid atmosphere.

Wallace, W. T.↗
DOE OSTI2020

A Systematic Evidence Based Performance Approach to Regulation of Nuclear Sites in England and Wales - 20058

The Environment Agency for England has developed a systematic evidence-based approach to pursue our strategic environmental objectives for the regulation of nuclear sites. We use an annual evidence review process to ensure effective and efficient targeting of limited resources to achieve those objectives. Over the last 8 years, we have been developing and refining this approach to ensure risk-based and value driven regulation. The approach comprises nuclear site and nuclear sector review processes known as Site Environment Review (SER) and Nuclear Environment Review (NER). This approach complements our regulation of nuclear site permit holders under the Environmental Permitting Regulations (EPR). We deliver our regulation of nuclear sites in England and Wales alongside the Office for Nuclear Regulation. The SER process involves the lead regulator for each nuclear site assessing the permit holder's environmental performance across 14 themes, set within the context of the site's main activities and associated waste disposals. Our themes include environmental leadership, resources and climate change, radioactive waste management, facility management and decommissioning, groundwater, and environmental radiological protection. We use evidence from site inspections and working within our subject matter groups to grade current and predicted future environmental performance. We are particularly interested in sustainability and the application of Best Available Techniques (BAT) to prevent the creation, and minimise the disposal, of radioactive wastes. We use risk analysis (strengths, weaknesses, threats and opportunities) to examine performance against our strategic environmental objectives, which are set out, in our 5-year Nuclear Delivery Plan (NDP). The output supports the targeting of our resources at each nuclear site. We consult the relevant permit holders on the SER priorities and use their feedback to refine our plans. We expect all permit holders to take account of our priorities when considering their own programmes of work, objectives and plans. The NER process brings together what we learn and achieve through regulation across the sector. It provides input to planning priorities, supported by qualitative and semi-quantitative evidence. It covers the 28 nuclear sites in England and Wales and spans the same 14 environmental themes. During the process we collate, compile and summarise evidence from the SERs and other sources such as inspection reports and evidence from our other nuclear work programmes. The output is the NER annual report. This provides a snapshot of the status of the nuclear sector and gives insights to enable us to regulate more efficiently and effectively. It also takes account of cross-cutting issues and risks such as changes in international standards, domestic policy, regulatory framework, domestic standards and guidance, learning from experience such as incidents, events and good practice, and innovation, research and development. It provides graphics that illustrate the grading of environmental performance for the nuclear sector across the fourteen environmental themes. This analysis allows benchmarking of nuclear site's environmental performance and the visualisation provides a convenient comparison of performance across themes, sites, and over time. We use this intelligence to inform our investment in training and development of our staff, and our cross-cutting engagement on strategic issues with government, the Nuclear Decommissioning Authority (NDA) and other corporate organisations. Adopting this approach can provide benefits with organisational reputation, stakeholder participation and ensuring value from the public investment. This paper describes the history of the SER/NER process, a selection of outputs from the process and ideas for improvement. The paper will be of interest to other regulators and organisations across the world that are interested in supporting continuous improvement. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Characterization of ferredoxins involved in electron transfer pathways for nitrogen fixation implicates differences in electronic structure in tuning 2[4Fe 4S] Fd activity

Ferredoxins (Fds) are small proteins which shuttle electrons to pathways like biological nitrogen fixation. Physical properties tune the reactivity of Fds with different pathways, but knowledge on how these properties can be manipulated to engineer new electron transfer pathways is lacking. Recently, we showed that an evolved strain of Rhodopseudomonas palustris uses a new electron transfer pathway for nitrogen fixation. This pathway involves a variant of the primary Fd of nitrogen fixation in R. palustris, Fer1, in which threonine at position 11 is substituted for isoleucine (Fer1 T11I ). To understand why this substitution in Fer1 enables more efficient electron transfer, we used in vivo and in vitro methods to characterize Fer1 and Fer1 T11I . Electrochemical characterization revealed both Fer1 and Fer1 T11I have similar redox transitions (–480 mV and – 550 mV), indicating the reduction potential was unaffected despite the proximity of T11 to an iron-sulfur (Fe—S) cluster of Fer1. Additionally, disruption of hydrogen bonding around an Fe—S cluster in Fer1 by substituting threonine with alanine (T11A) or valine (T11V) did not increase nitrogenase activity, indicating that disruption of hydrogen bonding does not explain the difference in activity observed for Fer1 T11I . Electron paramagnetic resonance spectroscopy studies revealed key differences in the electronic structure of Fer1 and Fer1 T11I , which indicate changes to the high spin states and/or spin-spin coupling between the Fe—S clusters of Fer1. Finally, our data implicates these electronic structure differences in facilitating electron flow and sets a foundation for further investigations to understand the connection between these properties and intermolecular electron transfer.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Radical SAM enzymes: Nature's choice for radical reactions

Enzymes that use a [4Fe-4S] 1+ cluster plus S-adenosyl-L-methionine (SAM) to initiate radical reactions (radical SAM) form the largest enzyme superfamily, with over half a million members across the tree of life. This review summarizes recent work revealing the radical SAM reaction pathway, which ultimately liberates the 5´-deoxyadenosyl (5´-dAdo•) radical to perform extremely diverse, highly regio- and stereo-specific, transformations. Most surprising was the discovery of an organometallic intermediate Ω exhibiting an Fe-C5´-adenosyl bond. Ω liberates 5´-dAdo• through homolysis of the Fe-C5´ bond, in analogy to Co-C5´ bond homolysis in B12, previously viewed as biology’s paradigmatic radical generator. The 5´-dAdo• has been trapped and characterized in radical SAM enzymes via a recently-discovered photoreactivity of the [4Fe- 4S] + /SAM complex, and has been confirmed as a catalytically active intermediate in enzyme catalysis. The regioselective SAM S-C bond cleavage to produce 5´-dAdo• originates in the JahnTeller effect. The simplicity of SAM as a radical precursor, and the exquisite control of 5´-dAdo• reactivity in radical SAM enzymes, may be why radical SAM enzymes pervade the tree of life, while B12 enzymes are only a few.

deoxyadenosyl radical↗
DOE OSTI2021

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites

Supercages of faujasite (FAU)-type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo 2 S 4 ) and tetranuclear (Mo 4 S 4 ) molybdenum sulfide clusters. The FAU-encaged Mo 4 S 4 clusters have a distorted cubane structure similar to the FeMo-cofactor in nitrogenase. Both clusters possess one unpaired electron per Mo atom. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stable (> 150 h) for ethene hydrogenation, while layered MoS 2 structures deactivate significantly under the same reaction conditions.

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

In situ detection of ferric reductase activity in the intestinal lumen of an insect

The rise of atmospheric oxygen as a result of photosynthesis in cyanobacteria and chloroplasts has transformed most environmental iron into the ferric state. In contrast, cells within organisms maintain a reducing internal milieu and utilize predominantly ferrous iron. Ferric reductases are enzymes that transfer electrons to ferric ions, either extracellularly or within endocytic vesicles, enabling cellular ferrous iron uptake through Divalent Metal Transporter 1. In mammals, duodenal cytochrome b is a ferric reductase of the intestinal epithelium, but how insects reduce and absorb dietary iron remains unknown. Here we provide indirect evidence of extracellular ferric reductase activity in a small subset of Drosophila melanogaster intestinal epithelial cells, positioned at the neck of the midgut’s anterior region. Dietary-supplemented bathophenanthroline sulphate (BPS) captures locally generated ferrous iron and precipitates into pink granules, whose chemical identity was probed combining in situ X-ray absorption near edge structure and electron paramagnetic resonance spectroscopies. An increased presence of manganese ions upon BPS feeding was also found. Control animals were fed with ferric ammonium citrate, which is accumulated into ferritin iron in distinct intestinal subregions suggesting iron trafficking between different cells inside the animal. Spectroscopic signals from the biological samples were compared to purified Drosophila and horse spleen ferritin and to chemically synthesized BPS-iron and BPS-manganese complexes. The results corroborated the presence of BPS-iron in a newly identified ferric iron reductase region of the intestine, which we propose constitutes the major site of iron absorption in this organism.

EPR↗
DOE OSTI2022

Primary donor triplet states of Photosystem I and II studied by Q-band pulse ENDOR spectroscopy

The photoexcited triplet state of the “primary donors” in the two photosystems of oxygenic photosynthesis has been investigated by means of electron-nuclear double resonance (ENDOR) at Q-band (34 GHz). The data obtained represent the first set of 1 H hyperfine coupling tensors of the 3 P700 triplet state in PSI and expand the existing data set for 3 P680. We achieved an extensive assignment of the observed electron-nuclear hyperfine coupling constants (hfcs) corresponding to the methine α-protons and the methyl group β-protons of the chlorophyll (Chl) macrocycle. The data clearly confirm that in both photosystems the primary donor triplet is located on one specific monomeric Chl at cryogenic temperature. In comparison to previous transient ENDOR and pulse ENDOR experiments at standard X-band (9–10 GHz), the pulse Q-band ENDOR spectra demonstrate both improved signal-to-noise ratio and increased resolution. The observed ENDOR spectra for 3 P700 and 3 P680 differ in terms of the intensity loss of lines from specific methyl group protons, which is explained by hindered methyl group rotation produced by binding site effects. Contact analysis of the methyl groups in the PSI crystal structure in combination with the ENDOR analysis of 3 P700 suggests that the triplet is located on the Chl a' (P A ) in PSI. The results also provide additional evidence for the localization of 3 P680 on the accessory Chl D1 in PSII.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Patient mutations in human ATP:cob(I)alamin adenosyltransferase differentially affect its catalytic versus chaperone functions

Human ATP:cob(I)alamin adenosyltransferase (ATR) is a mitochondrial enzyme that catalyzes an adenosyl transfer to cob(I)alamin, synthesizing 5'-deoxyadenosylcobalamin (AdoCbl) or coenzyme B 12 . ATR is also a chaperone that escorts AdoCbl, transferring it to methylmalonyl-CoA mutase, which is important in propionate metabolism. Mutations in ATR lead to methylmalonic aciduria type B, an inborn error of B12 metabolism. Our previous studies have furnished insights into how ATR protein dynamics influence redox-linked cobalt coordination chemistry, controlling its catalytic versus chaperone functions. In this study, we have characterized three patient mutations at two conserved active site residues in human ATR, R190C/H, and E193K and obtained crystal structures of R190C and E193K variants, which display only subtle structural changes. All three mutations were found to weaken affinities for the cob(II)alamin substrate and the AdoCbl product and increase K M(ATP) . 31 P NMR studies show that binding of the triphosphate product, formed during the adenosylation reaction, is also weakened. However, although the k cat of this reaction is significantly diminished for the R190C/H mutants, it is comparable with the WT enzyme for the E193K variant, revealing the catalytic importance of Arg-190. Furthermore, although the E193K mutation selectively impairs the chaperone function by promoting product release into solution, its catalytic function might be unaffected at physiological ATP concentrations. In contrast, the R190C/H mutations affect both the catalytic and chaperoning activities of ATR. Because the E193K mutation spares the catalytic activity of ATR, our data suggest that the patients carrying this mutation are more likely to be responsive to cobalamin therapy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A variant of the MenB strain of Synechocystis sp. PCC 6803 disrupts a stress response pathway allowing DMPBQ to occupy the A 1 sites of photosystem I

Phylloquinone (PhQ) plays a unique role in photosynthesis as the A1A and A1B intermediates in light-driven electron transfer in Photosystem I (PSI). When PhQ biosynthesis is inhibited by deletion of the menB gene in the cyanobacterium Synechocystis sp. PCC 6803, previous studies have shown that plastoquinone-9 (PQ-9) occupies the A 1 sites. However, a recent cryo-electron microscopy structure of a strain of ΔmenB from the year 2023 revealed an unusual quinone in the A 1 sites with a benzoquinone headgroup similar to PQ-9 and a phytyl tail similar to PhQ. Here, we investigate its biosynthesis and binding properties. Mass spectrometry confirms that PSI from the 2023 ΔmenB strain contains 2,3-dimethyl-5-phytyl-1,4-benzoquinone (DMPBQ), while PSI from the original strain contains PQ-9. Whole genome sequencing reveals that a mutation in slr1737 (tocopherol cyclase) leads to the accumulation of DMPBQ, an intermediate in the tocopherol biosynthetic pathway. Transient optical and electron paramagnetic resonance spectroscopy studies show that when DMPBQ occupies the A 1 sites, it does not exchange with exogenously supplied PhQ in contrast to PQ-9, which exchanges readily. We propose that the slr1737 mutation in the 2023 ΔmenB strain is a likely candidate for the source of the phenotype. This new strain has sacrificed tocopherol synthesis, the absence of which is known to have no effect on growth under low stress conditions, resulting in incorporation of DMPBQ in the A 1 sites. The tighter binding and function of DMPBQ likely allow this ΔmenB strain to outcompete its peers under optimal growth conditions and thus dominate the population.

2,3-dimethyl-5-phytyl-1,4-benzoquinone↗
DOE OSTI2020

Activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Here, activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO 2 and surface carbon adatoms, and adsorbs to form surface formate species. H 2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO 2 and H 2 , while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH 2 (a), CH 3 (a) and eventually gaseous CH 4 . The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH 4 . These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to N 2 reduction

Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by cadmium sulfide (CdS) nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model, which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of the sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway that competes with N 2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N 2 reduction.

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

Spin–Lattice Relaxation Decoherence Suppression in Vanishing Orbital Angular Momentum Qubits

Multifrequency electron paramagnetic resonance spectroscopy on oriented single crystals of magnetically dilute Gd(III) ions in Gd 0.004 Y 0.996 (trensal) is used to determine the Hamiltonian parameters of the ground 8 S 7/2 term and its phase memory time, Tm, characterizing its coherent spin dynamics. Here, the vanishing orbital angular momentum of the 8 S 7/2 term makes it relatively insensitive to spin–lattice relaxation mediated by magnetoelastic coupling and leads to a T m of 12 μs at 3 K, which is not limited by spin–lattice relaxation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Quantum Dot–Organic Molecule Conjugates as Hosts for Photogenerated Spin Qubit Pairs

The inherent spin polarization present in photogenerated spin-correlated radical pairs makes them promising candidates for quantum computing and quantum sensing applications. The spin states of these systems can be probed and manipulated with microwave pulses using electron paramagnetic resonance spectrometers. However, to date, there are no reports on magnetic resonance-based spin measurements of photogenerated spin-correlated radical pairs hosted on quantum dots. In the current work, we prepare dye molecule-inorganic quantum dot conjugates and show that they can produce photogenerated spin-polarized states. The dye molecule, D131, is chosen for its ability to undergo efficient charge separation, and the nanoparticle materials, ZnO quantum dots, are chosen for their promising spin properties. Transient and steady state optical spectroscopy performed on ZnO quantum dot-D131 conjugates shows that reversible photogenerated charge separation is occurring. Transient and pulsed electron paramagnetic resonance experiments are then performed on the photogenerated radical pair, which demonstrate that (1) the radical pair is polarized at moderate temperatures and well modeled by existing theories and (2) the spin states can be accessed and manipulated with microwave pulses. In conclusion, this work opens the door to a new class of promising qubit materials that can be photogenerated in polarized states and hosted by highly tailorable inorganic nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗