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DOE OSTI2023

A designed Copper Histidine-brace enzyme for oxidative depolymerization of polysaccharides as a model of lytic polysaccharide monooxygenase

The “Histidine-brace” (His-brace) copper-binding site, composed of Cu(His) 2 with a backbone amine, is found in metalloproteins with diverse functions. A primary example is lytic polysaccharide monooxygenase (LPMO), a class of enzymes that catalyze the oxidative depolymerization of polysaccharides, providing not only an energy source for native microorganisms but also a route to more effective industrial biomass conversion. Despite its importance, how the Cu His-brace site performs this unique and challenging oxidative depolymerization reaction remains to be understood. To answer this question, we have designed a biosynthetic model of LPMO by incorporating the Cu His-brace motif into azurin, an electron transfer protein. Spectroscopic studies, including ultraviolet-visible (UV–Vis) absorption and electron paramagnetic resonance, confirm copper binding at the designed His-brace site. Moreover, the designed protein is catalytically active towards both cellulose and starch, the native substrates of LPMO, generating degraded oligosaccharides with multiturnovers by C1 oxidation. It also performs oxidative cleavage of the model substrate 4-nitrophenyl-D-glucopyranoside, achieving a turnover number ~9% of that of a native LPMO assayed under identical conditions. This work presents a rationally designed artificial metalloenzyme that acts as a structural and functional mimic of LPMO, which provides a promising system for understanding the role of the Cu His-brace site in LPMO activity and potential application in polysaccharide degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2006

Complex Organic Materials on Planetary Satellites and Other Small Bodies of the Solar System

The search for organic materials on small bodies of the Solar System is conducted spectroscopically from Earth-based telescopes and from spacecraft. Although the carbonaceous meteorites carry a significant inventory of complex organic solids, the sources of these meteorites have not been identified. Infrared spectra of a sample of the suspected sources, the C- and D-class asteroids, including new data from the Spitzer Space Telescope, show signatures of silicates, but none diagnostic of organic compounds. In the absence of discrete spectral features, the low albedos and colors in the visible and near-IR spectral regions are the principal links between the organic-bearing meteorites and the asteroids. While Pluto and a few trans-neptunian objects show spectral signatures of frozen CH4. Solid CH3OH has been identified on two Centaur objects in the outer Solar System. In some cases the red colors of those objects suggest the presence of tholins. The VIMS instrument aboard the Cassini spacecraft in orbit around Saturn has detected near-IR spectral features on at least three of Saturn's satellites that are indicative or suggestive of organic molecules. One entire hemisphere of the satellite Iapetus is covered with low-albedo material that shows a spectral signature of aromatic hydrocarbons (3.3 microns) and the -CH2 stretching mode bands of an aliphatic component. Organics absorbing at 3.44 microns are suspected in the region of the south pole of Enceladus, and also on the surface of Phoebe. Organic material may originate on icy bodies in the current epoch by various processes of energy deposition into native material, or they may fall to the surface from an external (probably cometary) source. Some organic material may be pre-solar, having originated in the interstellar medium before the formation of the Solar System. Using the techniques of remote sensing, its detection and analysis are slow and difficult.

Cruikshank, Dale P.↗

DOE OSTI2022

Multi-crystal native-SAD phasing at 5 keV with a helium environment

De novo structure determination from single-wavelength anomalous diffraction using native sulfur or phosphorus in biomolecules (native-SAD) is an appealing method to mitigate the labor-intensive production of heavy-atom derivatives and selenomethionyl substitutions. The native-SAD method is particularly attractive for membrane proteins, which are difficult to produce and often recalcitrant to grow into decent-sized crystals. Native-SAD uses lower-energy X-rays to enhance anomalous signals from sulfur or phosphorus. However, at lower energies, the scattering and absorption of air contribute to the background noise, reduce the signals and are thus adverse to native-SAD phasing. We have previously demonstrated native-SAD phasing at an energy of 5 keV in air at the NSLS-II FMX beamline. Here, the use of a helium path developed to reduce both the noise from background scattering and the air absorption of the diffracted X-ray beam are described. The helium path was used for collection of anomalous diffraction data at 5 keV for two proteins: thaumatin and the membrane protein TehA. Although anomalous signals from each individual crystal are very weak, robust anomalous signals are obtained from data assembled from micrometre-sized crystals. The thaumatin structure was determined from 15 microcrystals and the TehA structure from 18 microcrystals. These results demonstrate the usefulness of a helium environment in support of native-SAD phasing at 5 keV.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1990

Energy balance components from six sites in a native prairie

The surface-flux stations investigated are of similar design and operation, but are located on different slopes and aspects and provided data with significant variations. The largest difference between sites is noticed in the data for soil heat-flux density, and the general variability is theorized to be related to treatment and locations. The number of surface-flux stations required for the prairie topography can be inferred from the results of the data analysis.

Fritschen, Leo J.↗

NASA NTRS1991

Ca-41 in iron falls, Grant and Estherville - Production rates and related exposure age calculations

Results are presented of the first phase of a Ca-41 cosmogenic studies program aimed at establishing baseline concentrations and trends in selected meteorites and the use of Ca-41 in estimating exposure ages and preatmospheric meteorite radii. The average Ca-41 saturation activity recorded in four small iron falls is 24 +/-1 dpm/kg. This finding, together with measurements at the center and surface of the large iron Grant, indicates that production of Ca-41 from spallation on iron is weakly dependent on shielding to depths as large as 250 g/sq cm. The (K-41)-Ca-41 exposure age of Grant is estimated at 330 +/-50 My, and an upper limit to its terrestrial age of 43 +/-15 ky. A comparison of the Ca-41 contents of stony and metallic material separated from the mesosiderite Estherville identifies low-energy neutron capture on native Ca as a second important channel of production. It is found that the Ca-41 signal in the stone phase from three meteorites correlates with their size, and that the inferred low-energy neutron fluxes vary by a factor of at least 20.

Fink, D.↗

DOE OSTI2022

Shifting from Fossil Fuel Reliance to Green Energy Sovereignty: Ute Mountain Ute Tribe

Self-determination has been an on-going effort for Native American people and gained much traction with the passing of The Energy Policy Act of 2005, which included the Indian Tribal Energy Development and Self-Determination Act. Congress passed this act to assist Native American tribes and Alaska Native villages with planning, development, and assistance to achieve their energy goals. The Ute Mountain Ute Tribe (UMUT) has relied on oil and natural gas for economic support the last 70 years. Burning fossil fuels, along with oil and gas development, decreases the quality of air and leads to increased greenhouse gas emissions. Subsequently, the burning of fossil fuels to produce energy is now more costly than many renewable energy sources, including solar photovoltaic (PV) systems. Environmental stewardship, along with the need to maintain revenue generation, has led UMUT’s efforts to achieve energy self-determinism employing PV and exploring other technology. In the past, the tribe completed a 1 megawatt PV project near Towaoc, Colorado, which serves as a case study on the tribe’s energy goals: a future where renewables will dominate their energy landscape. This paper explores UMUT’s past and on-going efforts toward energy independence and how it relates to the broader landscape of Native American energy sovereignty.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

NASA NTRS2009

Lunar Thermal Wadis and Exploration Rovers: Outpost Productivity and Participatory Exploration

The presentation introduces the concept of a thermal wadi, an engineered source of thermal energy that can be created using native material on the moon or elsewhere to store solar energy for use by various lunar surface assets to survive the extremely cold environment of the lunar night. A principal benefit of this approach to energy storage is the low mass requirement for transportation from Earth derived from the use of the lunar soil, or regolith, as the energy storage medium. The presentation includes a summary of the results of a feasibility study involving the numerical modeling of the performance of a thermal wadi including a manufactured thermal mass, a solar energy reflector, a nighttime thermal energy reflector and a lunar surface rover. The feasibility study shows that sufficient thermal energy can be stored using unconcentrated solar flux to keep a lunar surface rover sufficiently warm throughout a 354 hour lunar night at the lunar equator, and that similar approaches can be used to sustain surface assets during shorter dark periods that occur at the lunar poles. The presentation includes descriptions of a compact lunar rover concept that could be used to manufacture a thermal wadi and could alternatively be used to conduct a variety of high-value tasks on the lunar surface. Such rovers can be produced more easily because the capability for surviving the lunar night is offloaded to the thermal wadi infrastructure. The presentation also includes several concepts for operational scenarios that could be implemented on the moon using the thermal wadi and compact rover concepts in which multiple affordable rovers, operated by multiple terrestrial organizations, can conduct resource prospecting and human exploration site preparation tasks.

Sacksteder, Kurt↗

DOE OSTI2024

Technical Assistance Opportunities for Tribes

The National Renewable Energy Laboratory (NREL) offers many forms of technical assistance for Tribes to support local clean energy priorities and challenges. With broad support from the U.S. Department of Energy (DOE) and local partners, NREL provides technical expertise to enable data-driven, informed clean energy decision making. Technical assistance may address energy strategy, project financing, policy design and development, data analysis, economic development, infrastructure planning, energy justice, climate change, resilience, or other energy priorities. NREL has a long history of partnering with Tribes and Tribal organizations, including in Alaska Native Villages where the extreme Arctic climate poses unique energy challenges. NREL works directly with Tribes to find solutions that address their self-defined energy priorities, challenges, and goals.

Alaska native village↗

DOE OSTI2022

Respiratory energy demands and scope for demand expansion and destruction

Photosynthesis is the primary energy input to plants, but most plant metabolic processes are powered much or all of the time by ATP and NAD(P)H that come from respiratory oxidation of photosynthetically produced carbohydrates, that is, “dark respiration” (Amthor, 1994). The processes of growth, nutrient uptake and assimilation, active transport, and maintenance are thus all clients of respiration and compete for their share of a respiratory energy budget that is capped by photosynthate income. The economic principle of opportunity cost applies to these clients’ competing demands: spending respiratory energy on process A means missing the benefit of investing that energy in process B (Mahmoudabadi et al., 2019). This principle is key to assessing prospects for crop improvement by metabolic engineering. As de Lorenzo (2015) put it: “metabolism…frames and ultimately resolves whether a given genetic program (existing…or engineered) can be deployed or not.” Foreign or reconfigured native processes bolted on to a crop-plant’s metabolic chassis must compete for respiratory energy with native ones without crashing the energy economy. A proviso on plant carbon budgets is that photosynthetic carbon fixation (“source activity”) can in certain cases increase to meet increased carbon demand (“sink activity”), that is, budget envelopes are not always fixed (Smith et al., 2018). However, as there is some consensus that productivity is most often limited or co-limited by carbon supply (Ainsworth and Long, 2005; Körner, 2015; Sonnewald and Fernie, 2018), we make this our basal assumption in the analyses below.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2026

High Penetration Solar and Battery Project in Noatak, Alaska

Through funding from the Department of Energy’s Office of Indian Energy, the Northwest Arctic Borough (NAB) and the Native Village of Noatak (NNV) formed a Tribal Energy Development Organization (TEDO) to implement the Noatak Solar and Battery Project to reduce reliance on costly imported diesel, stabilize energy costs, and strengthen local energy sovereignty.

14 SOLAR ENERGY↗

NASA NTRS2001

Transport Through Carbon Nanotube Wires

This viewgraph presentation deals with the use of carbon nanotubes as a transport system. Contact, defects, tubular bend, phonons, and mechanical deformations all contribute to reflection within the nanotube wire. Bragg reflection, however, is native to an ideal energy transport system. Transmission resistance depends primarily on the level of energy present. Finally, the details regarding coupling between carbon nanotubes and simple metals are presented.

Anantram, M. P.↗

DOE OSTI2026

Influence of cellular redox reactions on the structure and function of light harvesting and photosystems

Photosynthesis enables the conversion of one of the most abundant and free forms of energy, sunlight, into chemical bonds through the utilization of highly tailored protein complexes. These enzymes work in unison to absorb, convert, and transform light into high-energy electrons which are used for various functions important to metabolism and cellular protection. Over the last ∼50 years, photosynthetic organisms, such as cyanobacteria, have been adapted and engineered to produce valuable compounds like hydrogen and ethylene, among others. Often this is performed by removing native and/or adding in exogenous energy utilization pathways so that light energy is re-directed towards the synthesis of desired compounds. However, the interplay between primary light capture, conversion reactions, and the downstream electron utilization sinks is not fully understood. Further complicating these strategies are the plethora of compensatory mechanisms that facilitate steady electron flow and the maintenance of photosynthesis under dynamic conditions. This manifests as structural and functional plasticity of the photosynthetic machinery, often seen in modulations of oligomeric compositions or changes in protein-protein interactions and coupling with redox enzymes. Understanding these mechanisms is crucial to biotechnology applications because re-engineering electron utilization sinks has profoundly different effects on the light capture and conversion reactions of photosynthesis. Optimization requires a molecular-level understanding of the functional interrelationships between electron sinks and photosynthetic components that influence photosynthetic efficiencies to realize potential improvements in product yields. Here, we aim to highlight how perturbation of reductive reactions is revealing the functional plasticity in key components of the photosynthetic energy transduction pathway.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2026

Project Phase 1 Report: Reducing Data Center Peak Cooling Demand and Energy Costs With Cold Underground Thermal Energy Storage (Cold UTES)

Cold Underground Thermal Energy Storage (Cold UTES) is an ultra-long duration grid energy storage technology. With Cold-UTES, low-cost grid power is converted to cold thermal energy and stored in the native subsurface rock at the point of use. Cold UTES is one approach within the general category of engineered geothermal systems. Cold UTES for peak-hour cooling of data centers (DCs) was studied for deployment in Maricopa County, Arizona and Loudoun County, Virgina using thermal storage capacities from 4 GWh-th to over 1,000 GWh-th (>1 Terawatt-hour). The two sites have different power and transmission systems, available grid energy resources, daily and seasonal load profiles, weather conditions, and grid regulatory requirements. The study results indicate high value for both locations and because of this, likely indicates value across most of the US and the world. The basis of the study was a 1,000 MW-e hourly electric use of DC computing and auxiliary loads, which was modeled as 1 GW-th of thermal load to a dry cooled heat rejection system - i.e. a cooling system that does not consume water. The electric power required for cooling the DC varies as the air temperature changes. In cold weather only the dry-coolers are used, with an electrical load for cooling load as low as 10 MW-e. In hot summer hours, chillers and dry- coolers are required, which raises the electrical load for cooling load to as much as 300 MW-e. The continuous and peak cooling electrical loads result in a grid interconnection requirement of no less than 1,300 MW-e. From both a grid and thermal design modeling perspective the 1.3 GW-e could either be a single facility or result from the total load at multiple sites.

15 GEOTHERMAL ENERGY↗

DOE OSTI2022

The major trimeric antenna complexes serve as a site for qH-energy dissipation in plants

Plants and algae are faced with a conundrum: harvesting sufficient light to drive their metabolic needs while dissipating light in excess to prevent photodamage, a process known as nonphotochemical quenching. A slowly relaxing form of energy dissipation, termed qH, is critical for plants’ survival under abiotic stress; however, qH location in the photosynthetic membrane is unresolved. Here, we tested whether we could isolate subcomplexes from plants in which qH was induced that would remain in an energy-dissipative state. Interestingly, we found that chlorophyll (Chl) fluorescence lifetimes were decreased by qH in isolated major trimeric antenna complexes, indicating that they serve as a site for qH-energy dissipation and providing a natively quenched complex with physiological relevance to natural conditions. Next, we monitored the changes in thylakoid pigment, protein, and lipid contents of antenna with active or inactive qH but did not detect any evident differences. Finally, we investigated whether specific subunits of the major antenna complexes were required for qH but found that qH was insensitive to trimer composition. Because we previously observed that qH can occur in the absence of specific xanthophylls, and no evident changes in pigments, proteins, or lipids were detected, we tentatively propose that the energy-dissipative state reported here may stem from Chl–Chl excitonic interaction.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Modeling neutral defects in III-V ternary alloys with a special quasirandom structure: Analysis of As- and III-site point defects in InGaAs

While first-principles density functional theory modeling has become a vital tool to investigate defect properties in semiconductors, the lack of crystalline periodicity in pseudobinary random composition alloys, such as In 1−𝑥 ⁢Ga 𝑥 ⁢As, complicates such analyses. We present a simulation strategy to systematically take into account the variability in the local defect environment in order to predict statistical properties of neutral intrinsic defects in In 1−𝑥⁢ Ga 𝑥 ⁢As. We use a comprehensive sampling from a modest-sized 64-atom special quasirandom structure (SQS) to define a statistically representative set of defects, and use a 512-atom hypercell, a 2 × 2 × 2 supercell of SQS supercells, to achieve cell-size convergence. We articulate an equivalent site principle and describe how it constrains atomic chemical reference energies in computation of defect formation energies in pseudobinary alloys. A simple protocol for estimating reference energies for the Ga and In atoms sharing the III site succeeds in obtaining the equivalence of defects at Ga-sites and In sites in the SQS supercell, (<30 meV differences in average formation energies). For III-site defects, such as the As antisite As III , the statistical variability in formation energies is modest, ≈ 0.1–0.2 eV. The variability in formation energy at As-site defects, such as the As vacancy 𝑣 As , can be much larger, >1 eV. The As antisite is shown to be a low-energy defect and the most likely to be present in as-grown materials, just as in GaAs. All other defects are higher-energy defects unlikely to be important in native material, but potentially important in radiation-damaged material. With a strong variability in defect energies, especially on the As-site, explicit consideration of statistical variability due to compositional randomness will be imperative for meaningful and quantitative comparisons to experiment.

Density functional theory↗

DOE OSTI2022

Superoxide Dismutase 1 Folding Stability as a Target for Molecular Tweezers in SOD1-Related Amyotrophic Lateral Sclerosis

Protein misfolding and aggregation are hallmarks of many severe neurodegenerative diseases including Alzheimer's, Parkinson's and Huntington's disease. As a supramolecular ligand that binds to lysine and arginine residues, the molecular tweezer CLR01 was found to modify the aggregation pathway of disease-relevant proteins in vitro and in vivo with beneficial effects on toxicity. However, the molecular mechanisms of how tweezers exert these effects remain mainly unknown, hampering further drug development. Here, we investigate the modulation mechanism of unfolding and aggregation pathways of SOD1, which are involved in amyotrophic lateral sclerosis (ALS), by CLR01. Using a truncated version of the wildtype SOD1 protein, SOD1 bar , we show that CLR01 acts on the first step of the aggregation pathway, the unfolding of the SOD1 monomer. CLR01 increases, by ~10 °C, the melting temperatures of the A4V and G41D SOD1 mutants, which are commonly observed mutations in familial ALS. Molecular dynamics simulations and binding free energy calculations as well as native mass spectrometry and mutational studies allowed us to identify K61 and K92 as binding sites for the tweezers to mediate the stability increase. The data suggest that the modulation of SOD1 conformational stability is a promising target for future developments of supramolecular ligands against neurodegenerative diseases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Experimental and theoretical studies of native deep-level defects in transition metal dichalcogenides

Abstract Transition metal dichalcogenides (TMDs), especially in two-dimensional (2D) form, exhibit many properties desirable for device applications. However, device performance can be hindered by the presence of defects. Here, we combine state of the art experimental and computational approaches to determine formation energies and charge transition levels of defects in bulk and 2D MX 2 (M = Mo or W; X = S, Se, or Te). We perform deep level transient spectroscopy (DLTS) measurements of bulk TMDs. Simultaneously, we calculate formation energies and defect levels of all native point defects, which enable identification of levels observed in DLTS and extend our calculations to vacancies in 2D TMDs, for which DLTS is challenging. We find that reduction of dimensionality of TMDs to 2D has a significant impact on defect properties. This finding may explain differences in optical properties of 2D TMDs synthesized with different methods and lays foundation for future developments of more efficient TMD-based devices.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Native Defects Hybridization and Electronic Transport in Cu 2 Se–CuGaSe 2 Hierarchical Composites

Engineering the energy distribution of electronic defects in semiconductors can afford the coexistence of degenerate and nondegenerate transport behavior. By leveraging native defects in Cu 2 Se and CuGaSe 2 phases, the tunability of the concentration and energy distribution of active electronic defects in hierarchical (1-x)Cu 2 Se-(x)CuGaSe 2 composites is demonstrated. This study found that the electrical conductivity of various composites decreases with rising temperature indicating degenerate semiconducting behavior, whereas the carrier density increases with temperature, which is consistent with non-degenerate semiconductivity. Remarkably, this study found that while the carrier density and electrical conductivity drop with the increasing CuGaSe 2 content for samples with x ≤ 0.45 is consistent with an increase in the activation energy of “active” electronic defects, the sudden increase by 140% in the electrical conductivity and by 109% in the carrier density for near equimolar composition suggests the formation of a large density of electronic defects with lower activation energy. This unusual behavior is understood within the context of the hybridization of coexisting native electronic defects to form degenerate hybrid acceptor states with lower activation energy. The reported unique electronic transport can be leveraged for the development of more versatile electronic and optoelectronic devices with superior performance.

36 MATERIALS SCIENCE↗