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DOE OSTI2026

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Ligand‐induced CaMKIIα hub Trp403 flip, hub domain stacking, and modulation of kinase activity

Abstract γ‐Hydroxybutyric acid (GHB) analogs are small molecules that bind competitively to a specific cavity in the oligomeric CaMKIIα hub domain. Binding affects conformation and stability of the hub domain, which may explain the neuroprotective action of some of these compounds. Here, we describe molecular details of interaction of the larger‐type GHB analog 2‐(6‐(4‐chlorophenyl)imidazo[1,2‐b]pyridazine‐2‐yl)acetic acid (PIPA). Like smaller‐type analogs, PIPA binding to the CaMKIIα hub domain promoted thermal stability. PIPA additionally modulated CaMKIIα activity under sub‐maximal CaM concentrations and ultimately led to reduced substrate phosphorylation. A high‐resolution X‐ray crystal structure of a stabilized CaMKIIα (6x mutant) hub construct revealed details of the binding mode of PIPA, which involved outward placement of tryptophan 403 (Trp403), a central residue in a flexible loop close to the upper hub cavity. Small‐angle X‐ray scattering (SAXS) solution structures and mass photometry of the CaMKIIα wild‐type hub domain in the presence of PIPA revealed a high degree of ordered self‐association (stacks of CaMKIIα hub domains). This stacking neither occurred with the smaller compound 3‐hydroxycyclopent‐1‐enecarboxylic acid (HOCPCA), nor when Trp403 was replaced with leucine (W403L). Additionally, CaMKIIα W403L hub was stabilized to a larger extent by PIPA compared to CaMKIIα hub wild type, indicating that loop flexibility is important for holoenzyme stability. Thus, we propose that ligand‐induced outward placement of Trp403 by PIPA, which promotes an unforeseen mechanism of hub domain stacking, may be involved in the observed reduction in CaMKIIα kinase activity. Altogether, this sheds new light on allosteric regulation of CaMKIIα activity via the hub domain.

Biochemistry & Molecular Biology↗

DOE OSTI2024

Genetic and enzymatic characterization of Amy13E from Cellvibrio japonicus reclassifies it as a cyclodextrinase also capable of α-diglucoside degradation

ABSTRACT Cyclodextrinases are carbohydrate-active enzymes involved in the linearization of circular amylose oligosaccharides. Primarily thought to function as part of starch metabolism, there have been previous reports of bacterial cyclodextrinases also having additional enzymatic activities on linear malto-oligosaccharides. This substrate class also includes environmentally rare α-diglucosides such as kojibiose (α−1,2), nigerose (α−1,3), and isomaltose (α−1,6), all of which have valuable properties as prebiotics or low-glycemic index sweeteners. Previous genome sequencing of threeCellvibrio japonicusstrains adapted to utilize these α-diglucosides identified multiple, but uncharacterized, mutations in each strain. One of the mutations identified was in theamy13Egene, which was annotated to encode a neopullulanase. In this report, we functionally characterized this gene and determined that it in fact encodes a cyclodextrinase with additional activities on α-diglucosides. Deletion analysis ofamy13Efound that this gene was essential for kojibiose and isomaltose metabolism inC. japonicus. Interestingly, a Δamy13Emutant was not deficient for cyclodextrin or pullulan utilization inC. japonicus; however, heterologous expression of the gene inE. coliwas sufficient for cyclodextrin-dependent growth. Biochemical analyses found thatCjAmy13E cleaved multiple substrates but preferred cyclodextrins and maltose, but had no activity on pullulan. Our characterization of theCjAmy13E cyclodextrinase is useful for refining functional enzyme predictions in related bacteria and for engineering enzymes for biotechnology or biomedical applications. IMPORTANCE Understanding the bacterial metabolism of cyclodextrins and rare α-diglucosides is increasingly important, as these sugars are becoming prevalent in the foods, supplements, and medicines humans consume that subsequently feed the human gut microbiome. Our analysis of a cyclomaltodextrinase with an expanded substrate range is significant because it broadens the potential applications of the GH13 family of carbohydrate active enzymes (CAZymes) in biotechnology and biomedicine. Specifically, this study provides a workflow for the discovery and characterization of novel activities in bacteria that possess a high number of CAZymes that otherwise would be missed due to complications with functional redundancy. Furthermore, this study provides a model from which predictions can be made why certain bacteria in crowded niches are able to robustly utilize rare carbon sources, possibly to gain a competitive growth advantage.

Biotechnology & Applied Microbiology↗

DOE OSTI2024

Structural and Interactional Analysis of the Flavonoid Pathway Proteins: Chalcone Synthase, Chalcone Isomerase and Chalcone Isomerase-like Protein

Chalcone synthase (CHS) and chalcone isomerase (CHI) catalyze the first two committed steps of the flavonoid pathway that plays a pivotal role in the growth and reproduction of land plants, including UV protection, pigmentation, symbiotic nitrogen fixation, and pathogen resistance. Based on the obtained X-ray crystal structures of CHS, CHI, and chalcone isomerase-like protein (CHIL) from the same monocotyledon, Panicum virgatum, along with the results of the steady-state kinetics, spectroscopic/thermodynamic analyses, intermolecular interactions, and their effect on each catalytic step are proposed. In addition, PvCHI’s unique activity for both naringenin chalcone and isoliquiritigenin was analyzed, and the observed hierarchical activity for those type-I and -II substrates was explained with the intrinsic characteristics of the enzyme and two substrates. The structure of PvCHS complexed with naringenin supports uncompetitive inhibition. PvCHS displays intrinsic catalytic promiscuity, evident from the formation of p-coumaroyltriacetic acid lactone (CTAL) in addition to naringenin chalcone. In the presence of PvCHIL, conversion of p-coumaroyl-CoA to naringenin through PvCHS and PvCHI displayed ~400-fold increased Vmax with reduced formation of CTAL by 70%. Supporting this model, molecular docking, ITC (Isothermal Titration Calorimetry), and FRET (Fluorescence Resonance Energy Transfer) indicated that both PvCHI and PvCHIL interact with PvCHS in a non-competitive manner, indicating the plausible allosteric effect of naringenin on CHS. Significantly, the presence of naringenin increased the affinity between PvCHS and PvCHIL, whereas naringenin chalcone decreased the affinity, indicating a plausible feedback mechanism to minimize spontaneous incorrect stereoisomers. These are the first findings from a three-body system from the same species, indicating the importance of the macromolecular assembly of CHS-CHI-CHIL in determining the amount and type of flavonoids produced in plant cells.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Emerging Strategies for Modifying Lignin Chemistry to Enhance Biological Lignin Valorization

Biological lignin valorization represents a promising approach contributing to sustainable and economic biorefineries. Here, the low level of valuable lignin–derived products remains a major challenge hindering the implementation of microbial lignin conversion. Lignin's properties play a significant role in determining the efficiency of lignin bioconversion. To date, despite significant progress in the development of biomass pretreatment, lignin fractionation, and fermentation over the last few decades, little efforts have gone into identifying the ideal lignin substrates for an efficient microbial metabolism. In this Minireview, emerging and state–of–the–art strategies for biomass pretreatment and lignin fractionation are summarized to elaborate their roles in modifying lignin structure for bioconversion. Fermentation strategies aimed at enhancing lignin depolymerization for microbial utilization are systematically reviewed as well. With an improved understanding of the ideal lignin structure elucidated by comprehensive metabolic pathways and/or big data analysis, modifying lignin chemistry could be more directional and effective. Ultimately, together with the progress of fermentation process optimization, biological lignin valorization will become more competitive in biorefineries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfer (PCET) process in Photosystem II, here a benzimidazole-phenol (BIP) has been covalently attached to the 2,2'-bipyridyl ligand of [Ir(dF(CF 3 )ppy) 2 (bpy)][PF 6 ] (dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; bpy = 2,2'-bipyridyl). Excitation of the [Ir(dF(CF 3 )ppy) 2 (BIP-bpy)][PF 6 ] photocatalyst results in intramolecular PCET to form a charge-separated state with oxidized BIP. Subsequent reduction of methyl viologen dication (MV 2+ ), a substrate surrogate, by the reducing moiety of the charge separated species demonstrates that the inclusion of BIP significantly slows the charge recombination rate. The effect of ~24-fold slower charge recombination in a photocatalytic phthalimide ester reduction resulted in a greater than 2-fold increase in reaction quantum efficiency.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

A ligand discovery toolbox for the WWE domain family of human E3 ligases

The WWE domain is a relatively under-researched domain found in twelve human proteins and characterized by a conserved tryptophan-tryptophan-glutamate (WWE) sequence motif. Six of these WWE domain-containing proteins also contain domains with E3 ubiquitin ligase activity. The general recognition of poly-ADP-ribosylated substrates by WWE domains suggests a potential avenue for development of Proteolysis-Targeting Chimeras (PROTACs). Here, we present novel crystal structures of the HUWE1, TRIP12, and DTX1 WWE domains in complex with PAR building blocks and their analogs, thus enabling a comprehensive analysis of the PAR binding site structural diversity. Furthermore, we introduce a versatile toolbox of biophysical and biochemical assays for the discovery and characterization of novel WWE domain binders, including fluorescence polarization-based PAR binding and displacement assays, 15 N-NMR-based binding affinity assays and 19 F-NMR-based competition assays. Through these assays, we have characterized the binding of monomeric iso -ADP-ribose ( iso -ADPr) and its nucleotide analogs with the aforementioned WWE proteins. Finally, we have utilized the assay toolbox to screen a small molecule fragment library leading to the successful discovery of novel ligands targeting the HUWE1 WWE domain.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

The Significance of the 'Insignificant': Non-covalent Interactions in CO 2 Reduction Reactions with 3C-TM (TM=Sc-Zn) Single-Atom Catalysts

With energy shortages and excessive CO 2 emissions driving climate change, converting CO 2 into high-value-added products offers a promising solution for carbon recycling. We investigate CO 2 reduction reactions (CO2RR) catalyzed by 10 single-atom catalysts (SACs), incorporating weak non-covalent interactions, specifically lone pair-π and H-π interactions. The SACs, consisting of transition metals coordinated by three carbon atoms in a defective graphene substrate (3C-TM, TM=Sc-Zn), leverage these interactions to influence the energy fluctuations of intermediates and the limiting potentials of CO 2 RR, without altering the overall reaction pathway. Further, our findings show that SACs based on early transition metals (Sc, Ti, V, Cr) can serve as catalysts for C 1 products, including HCOOH, HCHO, CH 3 OH, and CH 4 , while those based on Fe and Co are suitable for CO formation. Driving force analysis helps bridge theoretical results with experimental observations and propose a modified approach for assessing hydrogen evolution reactions (HER) competition. SACs based on Ni and Cu exhibit moderate HER tolerance, while early transition metals excel in selective CO 2 reduction. We also identify a linear scaling relationship between the free energies of *COOH and *CO. This study offers valuable insights for future experimental studies and large-scale computational screenings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Time-Resolved Evolution of the 3D Nanoporous Structure of Sintered Ag by X-Ray Nanotomography: Role of the Interface with a Copper Substrate

Here, the evolution of the nanoporous structure of cylindrical sintered silver samples during high temperature aging, ranging from 200 to 350 °C for 350 min, is studied through in situ computed X-ray tomography. Investigations are carried out for two types of specimens: pure sintered silver and specimens containing a silver-copper interface. It is shown that the overall pore evolution is driven by the evolution of very few large ones. The smaller pores, although being more numerous, do not really evolve before being absorbed by the few bigger ones. In pure silver, pore evolution is driven by diffusion (Ostwald ripening) but the presence of an interface promotes faster growth kinetics until the aging time reaches a threshold value, after which a deviation from Ostwald ripening occurs. The transition is a function of the aging temperature. This behavior is associated with the competition between elastic relaxation and surface energy minimization.

42 ENGINEERING↗

DOE OSTI2020

Anomalous Behavior of 2D Janus Excitonic Layers under Extreme Pressures

Newly discovered 2D Janus transition metal dichalcogenides layers have gained much attention from a theory perspective owing to their unique atomic structure and exotic materials properties, but little to no experimental data are available on these materials. Here, experimental and theoretical studies establish the vibrational and optical behavior of 2D Janus S–W–Se and S–Mo–Se monolayers under high pressures for the first time. Chemical vapor deposition (CVD)-grown classical transition metal dichalcogenides (TMD) monolayers are first transferred onto van der Waals (vdW) mica substrates and converted to 2D Janus sheets by surface plasma technique, and then integrated into a 500 µm size diamond anvil cell for high-pressure studies. Overall, the results show that 2D Janus layers do not undergo phase transition up to 15 GPa, and in this pressure regime, their vibrational modes exhibit a nonmonotonic response to the applied pressures (dω/dP). Interestingly, these 2D Janus monolayers exhibit unique blueshift in photoluminescence (PL) upon compression, which is in contrast to many other traditional semiconductor materials. Overall theoretical simulations offer in-depth insights and reveal that the overall optical response is a result of competition between the ab-plane (blueshift) and c-axis (redshift) compression. The overall findings shed the very first light on how 2D Janus monolayers respond under extreme pressures and expand the fundamental understanding of these materials.

2D Janus monolayers↗

NASA NTRS1993

Study of the Staebler-Wronski degradation effect in a-Si:H based p-i-n solar cell

Conversion of solar energy into electricity using environmentally safe and clean photovoltaic methods to supplement the ever increasing energy needs has been a cherished goal of many scientists and engineers around the world. Photovoltaic solar cells on the other hand, have been the power source for satellites ever since their introduction in the early sixties. For widespread terrestrial applications, however, the cost of photovoltaic systems must be reduced considerably. Much progress has been made in the recent past towards developing economically viable terrestrial systems, and the future looks highly promising. Thin film solar cells offer cost reductions mainly from their low processing cost, low material cost, and choice of low cost substrates. These are also very attractive for space applications because of their high power densities (power produced per kilogram of solar cell pay load) and high radiation resistance. Amorphous silicon based solar cells are amongst the top candidates for economically viable terrestrial and space based power generation. Despite very low federal funding during the eighties, amorphous silicon solar cell efficiencies have continually been improved - from a low 3 percent to over 13 percent now. Further improvements have been made by the use of multi-junction tandem solar cells. Efficiencies close to 15 percent have been achieved in several labs. In order to be competitive with fossil fuel generated electricity, it is believed that module efficiency of 15 percent or cell efficiency of 20 percent is required. Thus, further improvements in cell performance is imperative. One major problem that was discovered almost 15 years ago in amorphous silicon devices is the well known Staebler-Wronski Effect. Efficiency of amorphous silicon solar cells was found to degrade upon exposure to sunlight. Until now their is no consensus among the scientists on the mechanism for this degradation. Efficiency may degrade anywhere from 10 percent to almost 50 percent within the first few months of operation. In order to improve solar cell efficiencies, it is clear that the cause or causes of such degradation must be found and the processing conditions altered to minimize the loss in efficiency. This project was initiated in 1987 to investigate a possible link between metallic impurities, in particular, Ag, and this degradation. Such a link was established by one of the NASA scientists for the light induced degradation of n+/p crystalline silicon solar cells.

Naseem, H. A.↗

DOE OSTI2020

Soil microbial function and fungal community data along an ectomycorrhizal basal area gradient, Vermont, May 2019

Mycorrhizal fungi can affect soil organic matter cycling through several mechanisms including priming, nutrient competition, and direct enzyme production. Differences in nutrient foraging strategies between ectomycorrhizal (EcM) and arbuscular mycorrhizal (AM) fungi produce divergent belowground dynamics: where EcM can take up organic nitrogen and directly break down SOM by producing enzymes, AM fungi are limited to scavenging mineral N. EcM-associated tree species also have leaf litter with relatively higher ratios of carbon to nitrogen (C:N), and belowground saprotrophic communities more dominated by fungi. Consequently, free-living microbes in EcM-dominated soils should experience nitrogen limitation, with subsequent increases in enzyme production and decreased carbon use efficiency (CUE). However, the relative importance of the effects of substrate quality and fungal community composition on enzyme production and CUE are unclear. To assess this distinction, we sampled the organic horizon and 10 cm of the mineral horizon in northern temperate forest soils along a gradient of EcM dominance (see SCxTS_DBH.csv for full tree species information). We characterized fungal community composition by measuring EcM relative abundances from extracted fungal DNA (To run raw ASV data through R code, use SCxTS_ASV_taxonomy.csv, and R code ITS_processing.Rmd; to see processed data with EcM relative abundance, use file SCxTS_sum_afitch_Feb18.20.csv) and the fungal to bacterial ratios (see data file SCxTS_plfa.csv) from phospholipid fatty acid analysis. Soil microbial functions were measured as potential activities of five hydrolytic and two oxidative enzymes ( To run raw data through R code us SCxTS_metadata.csv, hydrolytic_oxidative_raw.csv, MUBraw.csv, Enzyme_soilweight.csv, and incubationtime.csv, and R code SCxTS_enzymes.Rmd; to use Enzyme data ready to run through statistics code, use file Enzyme.data.csv) and microbial carbon use efficiency (see file SCxTS_CUE.csv and for full calculations file 18O_CUEcalcs_SCxTS_2019.xlsx). We assessed soil substrate quality as the soil carbon:nitrogen ratio (See file Organic_CN.csv). Statistical analysis can be run using R code from file SCxTS_analysis.Rmd.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Assessment of Offshore Wind Energy Leasing Areas for Humboldt and Morro Bay Wind Energy Areas, California

The National Renewable Energy Laboratory (NREL) is providing scientific and technical services to the Bureau of Ocean Energy Management (BOEM) under an interagency agreement. The purpose of this report is to provide technical assistance in delineating potential lease areas from the California wind energy areas (WEAs) that can be competitively auctioned to wind energy developers. Each wind energy area is presumed to be technically and economically feasible for wind energy development based on the economic cost study performed by NREL in 2020. The subsequent analysis summarized in this report is intended to help BOEM maximize efficient offshore wind energy resource use and ensure fair return to the Government for use of the lease areas, by making recommendations for viable ways to divide the WEAs into auctionable commercial lease areas of approximately equal value. We considered several factors that affect the value of lease areas for wind energy development, including mean wind speeds, water depth, seafloor gradient, seismicity, hard substrate, and access to infrastructure. The largest impact to generating capacity came from the choice of mooring technology and the resulting setback from the lease area boundaries. Based on our setback assumptions, the generating capacity for a wind plant using catenary moorings could be nearly 30% less than with vertical moorings in Humboldt, or approximately 20% less in Morro Bay. The likely range of generating capacity is 1.5 to 3 GW in Humboldt and 3 to 5 GW in Morro Bay.

17 WIND ENERGY↗

NASA NTRS1992

Trapping of noble gases in proton-irradiated silicate smokes

We have measured Ne, Ar, Kr, and Xe in Si2O3 'smokes' that were condensed on Al substrates, vapor-deposited with various mixtures of CH4, NH3, H2O3 and noble gases at 10 K and subsequently irradiated with 1 MeV protons to simulate conditions during grain mantle formation in interstellar clouds. Neither Ne nor Ar is retained by the samples upon warming to room temperature, but Xe is very efficiently trapped and retained. Kr is somewhat less effectively retained, typically depleted by factors of about 10-20 relative to Xe. Isotopic fractionation favoring the heavy isotopes of Xe and Kr of about 5-10-percent/amu is observed. Correlations between the specific chemistry of the vapor deposition and heavy noble gas retention are most likely the result of competition by the various species for irradiation-produced trapping sites. The concentration of Xe retained by some of these smokes exceeds that observed in phase Q of meteorites and, like phase Q, they do not seem to be carriers of the light noble gases.

Nichols, R. H., Jr.↗

NASA NTRS2012

Modular Flooring System

The modular flooring system (MFS) was developed to provide a portable, modular, durable carpeting solution for NASA fs Robotics Alliance Project fs (RAP) outreach efforts. It was also designed to improve and replace a modular flooring system that was too heavy for safe use and transportation. The MFS was developed for use as the flooring for various robotics competitions that RAP utilizes to meet its mission goals. One of these competitions, the FIRST Robotics Competition (FRC), currently uses two massive rolls of broadloom carpet for the foundation of the arena in which the robots are contained during the competition. The area of the arena is approximately 30 by 72 ft (approximately 9 by 22 m). This carpet is very cumbersome and requires large-capacity vehicles, and handling equipment and personnel to transport and deploy. The broadloom carpet sustains severe abuse from the robots during a regular three-day competition, and as a result, the carpet is not used again for competition. Similarly, broadloom carpets used for trade shows at convention centers around the world are typically discarded after only one use. This innovation provides a green solution to this wasteful practice. Each of the flooring modules in the previous system weighed 44 lb (.20 kg). The improvements in the overall design of the system reduce the weight of each module by approximately 22 lb (.10 kg) (50 %), and utilize an improved "module-to-module" connection method that is superior to the previous system. The MFS comprises 4-by-4-ft (.1.2-by- 1.2-m) carpet module assemblies that utilize commercially available carpet tiles that are bonded to a lightweight substrate. The substrate surface opposite from the carpeted surface has a module-to-module connecting interface that allows for the modules to be connected, one to the other, as the modules are constructed. This connection is hidden underneath the modules, creating a smooth, co-planar flooring surface. The modules are stacked and strapped onto durable, commercially available drywall carts for storage and/or transportation. This method of storage and transportation makes it very convenient and safe when handling large quantities of modules.

Thate, Robert↗

DOE OSTI2026

Interplay of ferromagnetic and antiferromagnetic interactions in epitaxial Co 3 ZnN

Antiperovskite nitrides with the general formula M 3 AN have attracted significant attention due to their tunable electronic and magnetic properties. Among them are many cobalt-based compounds predicted to exhibit high thermodynamic stability and intriguing magnetic behavior. Here, we report the synthesis and magnetic characterization of epitaxial Co3ZnN thin films grown by radio frequency sputtering on SrTiO 3 (STO) and MgO substrates. X-ray diffraction confirms phase-pure (00l)-oriented films with cube-on-cube epitaxy on STO, with a c-lattice parameter of 3.752 Å. Magnetic measurements reveal clear hysteresis at 2 K with a coercive field of ∼0.11 T and a small net moment of 0.108 μ B /f.u., suggesting either a canted antiferromagnetic (AFM) or ferrimagnetic (FiM) configuration. Temperature-dependent magnetization measurements show a transition near 25 K, with strong AFM interactions with Curie–Weiss temperature (Θ) = −80.13 K. Complementary density functional theory and Monte Carlo simulations indicate a ferromagnetic (FM) ground state, with the FM–AFM energy difference decreasing systematically with increasing supercell size, consistent with competition between FM and AFM/FiM interactions. These results highlight Co3ZnN as a magnetically complex antiperovskite nitride with competing exchange interactions.

36 MATERIALS SCIENCE↗

NASA NTRS1992

Styles of crater gradation in Southern Ismenius Lacus, Mars: Clues from Meteor Crater, Arizona

Impact craters on the Earth and Mars provide a unique opportunity to quantify the gradational evolution of instantaneously created landforms in a variety of geologic settings. Unlike most landforms, the initial morphology associated with impact craters on both planets is uncomplicated by competition between construction and degradation during formation. Furthermore, pristine morphologies are both well-constrained and similar to a first order. The present study compares styles of graduation at Meteor Crater with those around selected craters (greater than 1-2 km in diameter) in southern Ismenius Lacus. Emphasis is placed on features visible in images near LANDSAT TM resolution (30-50 m/pixel) which is available for both areas. In contrast to Mars, vegetation on the Earth can modify gradation, but appears to influence overall rates and styles by 2X-3X rather than orders of magnitude. Further studies of additional craters in differing settings will refine the effects of this and other factors (e.g., substrate). Finally, by analogy with results from other terrestrial gradational surfaces this study should help provide constraints on climate over crater histories.

Grant, J. A.↗

DOE OSTI2020

Engineering Catalysts for Selective Ester Hydrogenation

The development of efficient catalysts and processes for synthesizing functionalized (olefinic and/or chiral) primary alcohols and fluoral hemiacetals is currently needed. These are valuable building blocks for pharmaceuticals, agrochemicals, perfumes, and so forth. From an economic standpoint, bench-stable Takasago Int. Corp.’s Ru-PNP, more commonly known as Ru-MACHO, and Gusev’s Ru-SNS complexes are arguably the most appealing molecular catalysts to access primary alcohols from esters and H 2 . This work introduces economically competitive Ru-SNP(O) z complexes ( z = 0, 1), which combine key structural elements of both of these catalysts. In particular, the incorporation of SNP heteroatoms into the ligand skeleton was found to be crucial for the design of a more product-selective catalyst in the synthesis of fluoral hemiacetals under kinetically controlled conditions. Based on experimental observations and computational analysis, this paper further extends the current state-of-the-art understanding of the accelerative role of KO- t -C 4 H 9 in ester hydrogenation. Finally, it attempts to explain why a maximum turnover is seen to occur starting at ~25 mol % base, in contrast to only ~10 mol % with ketones as substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗