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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Charge trapping at Al/Al 2 ⁢O 3 interface facilitates hydrogen-induced superabundant metal vacancy formation

Hydrogen is a ubiquitous impurity that deteriorates the metal/oxide interface, causing challenges such as current leakage and blistering. Here, in this work, we uncover the mechanisms behind hydrogen-induced damage at the prototypical Al/A⁢l 2 ⁢O 3 interface. The precursor that we identify is charge trapping at the interface, which facilitates hydrogen segregation to the interface plane as H – . Presence of hydrogen increases aluminum vacancy concentration at the interfacial metal and oxide planes. Each Al vacancy can trap multiple hydrogen atoms. As a result, the interfacial aluminum vacancy and hydrogen concentrations increase by orders of magnitude. Additionally, hydrogen behaves as an n-type dopant and increases electronic conductivity at the oxide layer adjacent to the interface by forming H + , and the [V Al –H] complex is the predominant defect at this layer. These findings provide the precursor mechanisms of hydrogen-induced damage at the metal-oxide interfaces and have implications for advancing Al/A⁢l 2 ⁢O 3 –based coatings and electronic devices.

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

Catalyst design for small molecule activation of energy consequence

This project targets the conversion of ubiquitous small molecules (e.g. NO, CO, H 2 O) into viable precursors to synthetic fuels. Current state of the art catalyst design has not directly targeted transition metal complexes capable of mediating the multi-electron redox processes necessary to reduce the overpotential (energy loss) required achieve efficient activation of small molecule substrates. In this vein, a new strategy has been developed for the assembly of polynuclear architectures; allowing for the construction of tunable polymetallic centers that assemble easily within a pre-organized template (conferring stability, selectivity and tunability) that can effect multi-electron redox processes for reactions. Catalyst development has commenced with the following target design elements: (1) catalysts featuring multiple transition metal ions in the same reaction space to greatly expand accessible molecular redox capabilities; (2) catalysts are assembled in a polynucleating ligand framework that permits control over the cluster morphology as well as the local steric and electronic environment of the transition metal ions within the cluster. The high-tunability of the catalyst composition (metal content) and geometric flexibility has permitted a rigorous assessment of electronic-structure-to-function relationship to be developed, further guiding synthetic efforts to realize more potent catalysts. The numerous permutations possible showcase the high degree of generality to this approach with many synthetic handles to tune redox and reaction chemistry. Trinuclear complexes have been synthesized featuring homo- and hetero-trinuclear cores featuring a variety of first row transition metal ions (Cr→Ni). The molecular clusters have been shown to successfully mediate multi-electron redox processes in a cooperative fashion without requiring strong chemical reductants or oxidants. The reactive molecular complexes are being utilized to activate and breakdown the robust bonds within typical waste stream small molecules (e.g., greenhouse gases) and convert them into value-added commodity chemicals. Ultimately, the catalysts developed by this approach will be required to convert energy acquired via renewable resources (e.g., solar or wind) into synthetic fuels as an energy storage mechanism.

10 SYNTHETIC FUELS↗
DOE OSTI2023

Human cytochrome P450 17A1 structures with metabolites of prostate cancer drug abiraterone reveal substrate-binding plasticity and a second binding site

Abiraterone acetate is a first-line therapy for castration-resistant prostate cancer. This prodrug is deacetylated in vivo to abiraterone, which is a potent and specific inhibitor of cytochrome P450 17A1 (CYP17A1). CYP17A1 performs two sequential steps that are required for the biosynthesis of androgens that drive prostate cancer proliferation, analogous to estrogens in breast cancer. Abiraterone can be further metabolized in vivo on the steroid A ring to multiple metabolites that also inhibit CYP17A1. Despite its design as an active-site-directed substrate analog, abiraterone and its metabolites demonstrate mixed competitive/noncompetitive inhibition. To understand their binding, we solved the X-ray structures of CYP17A1 with three primary abiraterone metabolites. Despite different conformations of the steroid A ring and substituents, all three bound in the CYP17A1 active site with the steroid core packed against the I helix and the A ring C3 keto or hydroxyl oxygen forming a hydrogen bond with N202 similar to abiraterone itself. The structure of CYP17A1 with 3-keto, 5α-abiraterone was solved to 2.0 Å, the highest resolution to date for a CYP17A1 complex. This structure had additional electron density near the F/G loop, which is likely a second molecule of the inhibitor and which may explain the noncompetitive inhibition. Mutation of the adjacent Asn52 to Tyr positions its side chain in this space, maintains enzyme activity, and prevents binding of the peripheral ligand. Collectively, our findings provide further insight into abiraterone metabolite binding and CYP17A1 function.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2000

Piezoelectric Shunt Vibration Damping of F-15 Panel under High Acoustic Excitation

At last year's SPIE symposium, we reported results of an experiment on structural vibration damping of an F-15 underbelly panel using piezoelectric shunting with five bonded PZT transducers. The panel vibration was induced with an acoustic speaker at an overall sound pressure level (OASPL) of about 90 dB. Amplitude reductions of 13.45 and 10.72 dB were achieved for the first and second modes, respectively, using single- and multiple-mode shunting. It is the purpose of this investigation to extend the passive piezoelectric shunt-damping technique to control structural vibration induced at higher acoustic excitation levels, and to examine the controllability and survivability of the bonded PZT transducers at these high levels. The shunting experiment was performed with the Thermal Acoustic Fatigue Apparatus (TAFA) at the NASA Langley Research Center using the same F-15 underbelly panel. The TAFA is a progressive wave tube facility. The panel was mounted in one wall of the TAFA test section using a specially designed mounting fixture such that the panel was subjected to grazing-incidence acoustic excitation. Five PZT transducers were used with two shunt circuits designed to control the first and second modes of the structure between 200 and 400 Hz. We first determined the values of the shunt inductance and resistance at an OASPL of 130 dB. These values were maintained while we gradually increased the OASPL from 130 to 154 dB in 6-dB steps. During each increment, the frequency response function between accelerometers on the panel and the acoustic excitation measured by microphones, before and after shunting, were recorded. Good response reduction was observed up to the 148dB level. The experiment was stopped at 154 dB due to wire breakage from vibration at a transducer wire joint. The PZT transducers, however, were still bonded well on the panel and survived at this high dB level. We also observed shifting of the frequency peaks toward lower frequency when the OASPL was increased. Detailed experimental results will be presented.

Wu, Shu-Yau↗
DOE OSTI2022

Performance Advantaged ..beta..-Ketone Containing Polymers - Benefits in Manufacturing, Performance, and End-of-Life

Biomass derived chemicals can possess extended functionality, often in the form of heteroatoms like oxygen and nitrogen, that can enable performance advantaged properties in emergent materials. These performance advantages can manifest in multiple ways such as reduced manufacturing intensity, better performance, or enhanced end-of-life options. One illustrative example of this concept is ..beta..-ketoadipic acid (..beta..KA), a C6 dicarboxylic acid with a ketone in its backbone. ..beta..KA can be obtained via biological cultivation from aromatic compounds, sugars, and even waste plastics. When ..beta..KA is implemented into polymers, namely nylons, in place of adipic acid the overall material properties are increased. Specifically, the glass transition temperature (which is the measurement at which temperature a plastic softens) is increased by 69 degrees C and the water permeability is reduced by 20%. Molecular dynamic (MD) simulations reveal that the ..beta..-ketone in ..beta..KA leads to restricted movement across multiple backbone carbons when compared to adipic acid. Furthermore, MD simulations reveal that the ..beta..-ketone, when compared to no-ketone or an a-ketone, can lead to an increase in hydrogen bonding between neighboring chains. Both phenomena may help explain the molecular origin of the increases in polymer performance. When implemented into polyesters, namely PET, ..beta..KA can maintain the requisite performance while enabling enhanced degradation. Aside from performance advantages in thermomechanical performance, the production of ..beta..KA also is advantaged in its manufacturing. Although estimates for the minimum selling price (MSP) of ..beta..KA exceed adipic acid the manufacture of ..beta..KAwould reduce supply chain energy and GHG emissions by >50% and >30% respectively. Further TEA analysis reveals that the MSP of ..beta..KA is primarily driven by the feedstock cost while the capital expenditures are driven largely by fermentation costs. Overall, the work presented within will be illustrative of how biomass derived molecules, namely ..beta..KA, can manifest performance advantages across multiple benchmarks and may enable a path to market for biomass-derived materials.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗
DOE OSTI2025

Ir(hkl) Surface Electrochemistry in a Nonadsorbing Acidic Medium

The fundamental properties of electrochemical materials depend on the multiple and often complex interactions between electrode surface sites and electrolyte species at the electrochemical interface. Despite Iridium use in electrolyzer systems, much of its surface electrochemistry remains underexplored. This study investigates the surface electrochemistry of Ir(111), Ir(100), and Ir(110) surfaces in acidic media. Using cyclic voltammetry and CO charge displacement experiments, we establish the charge states and adsorbate coverages as a function of the electrode potential, revealing the presence of hydrogen and hydroxyl co-adsorption at low potentials on (111), and almost no coverage of H ad on (110) facet. In situ Shell Isolated Nanoparticle Enhanced Raman Spectroscopy experiments provide direct evidence of the formation of key adsorbate species, such as hydrogen, hydroxyl, and oxygen, but most importantly, their interactions with interfacial water, confirmed by Density Functional Theory calculations. Our findings highlight the role of co-adsorption and interspecies interactions, with microkinetic adsorption voltammetry simulations corroborating the influence of lateral interactions on adsorption dynamics, particularly for Ir(100) where the OHad formation occurs as a sharp adsorption/desorption current. Our results underscores the importance of interfacial water and hydrogen bonding networks in shaping the electrochemical behavior on Ir surfaces, refining our baseline understanding of the Ir surface electrochemistry necessary for the development of advanced Ir-based electrochemical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Ames Engineering Directorate

The Ames Engineering Directorate is the principal engineering organization supporting aerospace systems and spaceflight projects at NASA's Ames Research Center in California's Silicon Valley. The Directorate supports all phases of engineering and project management for flight and mission projects-from R&D to Close-out-by leveraging the capabilities of multiple divisions and facilities.The Mission Design Center (MDC) has full end-to-end mission design capability with sophisticated analysis and simulation tools in a collaborative concurrent design environment. Services include concept maturity level (CML) maturation, spacecraft design and trades, scientific instruments selection, feasibility assessments, and proposal support and partnerships. The Engineering Systems Division provides robust project management support as well as systems engineering, mechanical and electrical analysis and design, technical authority and project integration support to a variety of programs and projects across NASA centers. The Applied Manufacturing Division turns abstract ideas into tangible hardware for aeronautics, spaceflight and science applications, specializing in fabrication methods and management of complex fabrication projects. The Engineering Evaluation Lab (EEL) provides full satellite or payload environmental testing services including vibration, temperature, humidity, immersion, pressure/altitude, vacuum, high G centrifuge, shock impact testing and the Flight Processing Center (FPC), which includes cleanrooms, bonded stores and flight preparation resources. The Multi-Mission Operations Center (MMOC) is composed of the facilities, networks, IT equipment, software and support services needed by flight projects to effectively and efficiently perform all mission functions, including planning, scheduling, command, telemetry processing and science analysis.

Small Satellites↗
DOE OSTI2021

Unveiling the ambipolar carrier transport property of SnO 2–X for multiple-functional interlayers in perovskite solar cells

Tin oxides are the most promising electron transport layers in perovskite solar cells. An ambipolar carrier transport property has been recently demonstrated which enables a simple interconnection structure for all-perovskite tandem solar cells. However, the underlying mechanism for its ambipolar behavior is unclear which cannot be explained by the intrinsic defects in SnO 2-x . Here by using density functional theory calculations, we unveil the origin of the ambipolar carrier transport of non-stoichiometry SnO 2-x with a structure of SnO embedded in SnO 2 matrix. The hybridization of O 2p and Sn 5s orbitals of SnO introduces mid-gap states in the bandgap of SnO 2 , enabling hole transport property for SnO 2-x when x is > 0.2. Increasing the percentage of SnO in SnO 2-x significantly enhances the hole transport capability of SnO 2-x due to the enlarged Sn-O-Sn angles that increases orbital overlapping between O and Sn atoms, thus providing strategies for the further tuning of the carrier transport properties of SnO 2-x by compositional and structural designs.

14 SOLAR ENERGY↗
DOE OSTI2023

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Sulfurized Polyacrylonitrile for High-Performance Lithium–Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur’s Reduction Pathways and Hidden Li + Storage Mechanisms for Extra Discharge Capacity

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium–sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN’s lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN’s structural characteristics and lithiation mechanisms via computational approaches. Here, our models reproduce most experimental data regarding carbon’s graphitization level and conjugated ordering, sulfur–carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone’s electrochemical activity occurs via multiple C–Li and N–Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H 2 reactions at the H 2 O-Ru(0 0 0 1) interface

Catalytic reactions of biomass-derived phenolics and H 2 occur on transition metal surfaces via competitive C–O cleavage and ring saturation pathways, with both requiring multiple hydrogen addition events before forming their respective rate limiting transition states. These events are markedly affected by solvent chemical identity, with polar protic solvents ionizing hydrogen adatoms (H*) to interfacial protons (H + ) and opening up new catalytic routes. Here, we establish the reaction coordinate space for guaiacol-H 2 reactions on Ru(0 0 0 1) using density functional theory and describe the atomic-scale effect of a polar protic solvent, H 2 O. Coupled H + and H* attack leads to quasi-equilibrated enol and keto intermediates as the precursors for C–O cleavage and ring saturation, respectively. For C–O cleavage, H 2 O solvent enables a lower energy pathway via concomitant transfer of the hydroxyl H + to the methoxy oxygen during C–OCH 3 cleavage, forming a charge separated [Ru(s)–(C 6 H 5 O – )…(H + )…OCH 3 ] transition state and reducing the barrier by up to 0.8 eV as compared to unassisted C–OCH 3 cleavage. For ring saturation, H* attack onto an unsaturated meta carbon is rate limiting with no direct solvent participation, suggesting that protic polar solvents selectively promote the C–O cleavage pathway. Taken together, we show that activating guaiacol for either C–O bond cleavage or ring saturation product formation depends on the reactive hydrogen identity (H* or H + ), enol/keto isomerization equilibrium, and accessibility of the proton assisted Car–OCH 3 cleavage transition state. Here, all such factors are tunable via changes to the solvent or metal identity.

09 BIOMASS FUELS↗
NASA NTRS1998

Analysis and Testing of Plates with Piezoelectric Sensors and Actuators

Piezoelectric material inherently possesses coupling between electrostatics and structural dynamics. Utilizing linear piezoelectric theory results in an intrinsically coupled pair of piezoelectric constitutive equations. One equation describes the direct piezoelectric effect where strains produce an electric field and the other describes the converse effect where an applied electrical field produces strain. The purpose of this study is to compare finite element analysis and experiments of a thin plate with bonded piezoelectric material. Since an isotropic plate in combination with a thin piezoelectric layer constitutes a special case of a laminated composite, the classical laminated plate theory is used in the formulation to accommodated generic laminated composite panels with multiple bonded and embedded piezoelectric layers. Additionally, the von Karman large deflection plate theory is incorporated. The formulation results in laminate constitutive equations that are amiable to the inclusion of the piezoelectric constitutive equations yielding in a fully electro-mechanically coupled composite laminate. Using the finite element formulation, the governing differential equations of motion of a composite laminate with embedded piezoelectric layers are derived. The finite element model not only considers structural degrees of freedom (d.o.f.) but an additional electrical d.o.f. for each piezoelectric layer. Comparison between experiment and numerical prediction is performed by first treating the piezoelectric as a sensor and then again treating it as an actuator. To assess the piezoelectric layer as a sensor, various uniformly distributed pressure loads were simulated in the analysis and the corresponding generated voltages were calculated using both linear and nonlinear finite element analyses. Experiments were carried out by applying the same uniformly distributed loads and measuring the resulting generated voltages and corresponding maximum plate deflections. It is found that a highly nonlinear relationship exists between maximum deflection and voltage versus pressure loading. In order to assess comparisons of predicted and measured piezoelectric actuation, sinusoidal excitation voltages are simulated/applied and maximum deflections are calculated/measured. The maximum deflection as a function of time was determined using the linear finite elements analysis. Good correlation between prediction and measurement was achieved in all cases.

Bevan, Jeffrey S.↗
DOE OSTI2024

Understanding Process–Structure Relationships during Lamination of Halide Perovskite Interfaces

Fabrication of halide perovskite (HP) solar cells typically involves the sequential deposition of multiple layers to create a device stack, which is limited by the thermal and chemical incompatibility of top contact layers with the underlying HP semiconductor. One emerging strategy to overcome these restrictions on material selection and processing conditions is lamination, where two half-stacks are independently processed and then diffusion bonded to complete the device. Lamination reduces the processing constraints on the top side of the solar cell to allow new device designs, expanded use of deposition methods, and self-encapsulation of devices. While laminated perovskite solar cells with high efficiencies and novel interlayer combinations have been demonstrated, there is a limited understanding of how the lamination process parameters affect the diffusion-bond quality and material properties of the resulting HP layer. In this study, we systematically vary temperature, pressure, and time during lamination and quantify the resulting impacts on bonded area, grain domain size, and photoluminescence. A design of experiments is performed, and statistical analysis of the experimental results is used to quantitatively evaluate the resulting process–structure–property relationships. The lamination temperature is found to be the key parameter controlling these properties. Furthermore, a temperature of 150 °C enables successful bonding over 95% of the substrate area and also results in increases in apparent grain domain size and photoluminescence intensity. Based on these insights, the lamination temperature of functional perovskite solar cell devices is varied, demonstrating the importance of the resulting bond quality on device performance metrics.

14 SOLAR ENERGY↗
DOE OSTI2022

Multi-reward Reinforcement Learning Based Bond-Order Potential to Study Strain-Assisted Phase Transitions in Phosphorene

Here, we introduce a multi-reward reinforcement learning (RL) approach to train a flexible bond-order potential (BOP) for 2D phosphorene based on ab initio training data sets. Our approach is based on a continuous action space Monte Carlo tree search algorithm that is general and scalable and presents an efficient multiobjective optimization scheme for high-dimensional materials design problems. As a proof-of-concept, we deploy this scheme to parametrize multiple structural and dynamical properties of 2D phosphorene polymorphs. Our RL-trained BOP model adequately captures the structure, energetics, transformation barriers, equation of state, elastic constants, and phonon dispersions of various 2D P polymorphs. We use this model to probe the impact of temperature and strain rate on the phase transition from black (α-P) to blue phosphorene (β-P) through molecular dynamics simulations. A decrease in critical strain for this phase transition with increase in temperature is observed, and the underlying atomistic mechanisms are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C 3+ Olefin Formation from Ethanol

Direct and selective production of C 3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C 3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H 2 ) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10 –3 mol mol Y –1 s –1 vs 1.2 × 10 –3 mol mol Zn –1 s –1 ). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C 3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.

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

KARRIKIN INSENSITIVE2 regulates leaf development, root system architecture and arbuscular‐mycorrhizal symbiosis in Brachypodium distachyon

SUMMARY KARRIKIN INSENSITIVE2 (KAI2) is an α/β‐hydrolase required for plant responses to karrikins, which are abiotic butenolides that can influence seed germination and seedling growth. Although represented by four angiosperm species, loss‐of‐function kai2 mutants are phenotypically inconsistent and incompletely characterised, resulting in uncertainties about the core functions of KAI2 in plant development. Here we characterised the developmental functions of KAI2 in the grass Brachypodium distachyon using molecular, physiological and biochemical approaches. Bdkai2 mutants exhibit increased internode elongation and reduced leaf chlorophyll levels, but only a modest increase in water loss from detached leaves. Bdkai2 shows increased numbers of lateral roots and reduced root hair growth, and fails to support normal root colonisation by arbuscular‐mycorrhizal (AM) fungi. The karrikins KAR 1 and KAR 2 , and the strigolactone (SL) analogue rac ‐GR24, each elicit overlapping but distinct changes to the shoot transcriptome via BdKAI2. Finally, we show that BdKAI2 exhibits a clear ligand preference for desmethyl butenolides and weak responses to methyl‐substituted SL analogues such as GR24. Our findings suggest that KAI2 has multiple roles in shoot development, root system development and transcriptional regulation in grasses. Although KAI2‐dependent AM symbiosis is likely conserved within monocots, the magnitude of the effect of KAI2 on water relations may vary across angiosperms.

Meng, Yongjie↗
NASA NTRS2016

Thermal Management and Thermal Protection Systems

During my internship in the Thermal Design Branch (ES3), I contributed to two main projects: i) novel passive thermal management system for future human exploration, ii) AVCOAT undercut thermal analysis. i) As NASA prepares to further expand human and robotic presence in space, it is well known that spacecraft architectures will be challenged with unprecedented thermal environments. Future exploration activities will have the need of thermal management systems that can provide higher reliability, mass and power reduction and increased performance. In an effort to start addressing the current technical gaps the NASA Johnson Space Center Passive Thermal Discipline has engaged in technology development activities. One of these activities was done through an in-house Passive Thermal Management System (PTMS) design for a lunar lander. The proposed PTMS, functional in both microgravity and gravity environments, consists of three main components: a heat spreader, a novel hybrid wick Variable Conductance Heat Pipe (VCHP), and a radiator. The aim of this PTMS is to keep electronics on a vehicle within their temperature limits (0 and 50 C for the current design) during all mission phases including multiple lunar day/night cycles. The VCHP was tested to verify its thermal performance. I created a thermal math model using Thermal Desktop (TD) and analyzed it to predict the PTMS performance. After testing, the test data provided a means to correlate the thermal math model. This correlation took into account conduction and convection heat transfer, representing the actual benchtop test. Since this PTMS is proposed for space missions, a vacuum test will be taking place to provide confidence that the system is functional in space environments. Therefore, the model was modified to include a vacuum chamber with a liquid nitrogen shroud while taking into account conduction and radiation heat transfer. Infrared Lamps were modelled and introduced into the model to simulate the sun's rays directly impinging on the system. Heating rate of the lamps were calculated by knowing fraction of emitted energy in a wavelength interval and the filament temperature. This version of the model can be used to predict performance of the system under vacuum with extreme cold or hot conditions. Initial testing of the PTMS showed promise, and the thermal math model predicts even better performance in thermal vacuum testing. ii) Thermal Protection Systems (TPS) are required for vehicles which enter earth's atmosphere to protect from aerodynamic heating caused by the friction between the vehicle and atmospheric gases. Orion's heat shield design has two aspects which needed to be analyzed thermally: i) a small excess of adhesive used to bond the outer AVCOAT layer to the inner composite structure tends to seep from under the AVCOAT and form a small bead in between two bricks of AVCOAT, ii) a silicone rubber with different thermophysical properties than AVCOAT fills the gap between two bricks of AVCOAT. I created a thermal model using TD to determine temperature differences that are caused by these two features. To prevent false results, all TD models must be verified against something known. In this case, the TD model was correlated to CHAR, an ablation modelling software used to analyze TPS. Analyzing a node far from the concerning features, we saw that the TD model data match CHAR data, verifying the TD model. Next, the temperature of the silicone rubber as well as the bead of adhesive were analyzed to determine if they exceeded allowable temperatures. It was determined that these two features do not have a significant effect on the max temperature of the heat shield. This model can be modified to check temperatures at various locations of the heat shield where the composite thickness varies.

Hasnain, Aqib↗
DOE OSTI2020

One Electron Multiple Proton Transfer in Model Organic Donor–Acceptor Systems: Implications for High-Frequency EPR

EPR spectroscopy is an important spectroscopic method for identification and characterization of radical species involved in many biological reactions. The tyrosyl radical is one of the most studied amino acid radical intermediates in biology. Often in conjunction with histidine residues, it is involved in many fundamental biological electron and proton transfer processes, such as in the water oxidation in photosystem II. As biological processes are typically extremely complicated and hard to control, molecular bio-mimetic model complexes are often used to clarify the mechanisms of the biological reactions. In this work, we present theoretical calculations to investigate the sensitivity of magnetic resonance parameters to proton-coupled electron transfer events, as well as conformational substates of the molecular constructs which mimic the tyrosine-histidine (Tyr-His) pairs found in a large variety of proteins. Upon oxidation of the phenol, the Tyr analog, these complexes can perform not only one-electron one-proton transfer (EPT), but also one-electron two-proton transfers (E2PT). It is shown that in aprotic environment the g X -components of the electronicg-tensor are extremely sensitive to the first proton transfer from the phenoxyl oxygen to the imidazole nitrogen (EPT product), leading to a significant increase of the g X -value of up to 0.003, but are not sensitive to the second proton transfer (E2PT). In the latter case, the change of the g X -value is much smaller (ca. 0.0001), which is too small to be distinguished even by high-frequency EPR. The 14 N hyperfine values are also too similar to allow differentiation between the different protonation states in EPT and E2PT. The magnetic resonance parameters were also calculated as a function of the rotation angles around single bonds. It was demonstrated that rotation of the phenoxyl group results in large positive changes (> 0.001) in the g X -values. Analysis of the data reveals that the main source of these changes is related to the strength of the H-bond between phenoxyl oxygen and the proton(s) on N 1 and N 2 positions of the imidazole.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗