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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Plasma-Catalyst Reactivity Control of Surface Nitrogen Species through Plasma-Temperature-Programmed Hydrogenation to Ammonia

Nonthermal plasma activation of N 2 can facilitate nitrogen adsorption on metal catalysts at low bulk temperatures and atmospheric pressure. Here, we apply a plasma-assisted temperature-programmed reaction (plasma-TPRxn) for ammonia (NH 3 ) synthesis using sequential exposure of a silica-supported metal catalyst to N 2 plasma followed by thermal hydrogen treatment while ramping the temperature to decouple the plasma activation of N 2 from surface catalyzed hydrogenation steps. This approach eliminates the effects from bulk plasma phase reactions, thereby allowing for direct interrogation of plasma activated nitrogen on the active metal surfaces. We confirm previously reported spectroscopic observations that show plasma-generated surface nitrogen can be converted to NH 3 through surface catalyzed pathways. Further, we demonstrate that the ammonia desorption peak temperature is sensitive to metal, with Pt desorbing NH 3 at the lowest temperature. Unsteady state microkinetic models of desorption kinetics as a function of initial N coverage and metal recover observed trends in NH 3 desorption temperatures and confirm that observed results reflect hydrogenation of plasma-induced N accommodation at each surface. In total, we show that the hydrogenation ability of the catalyst after plasma activation of N 2 is responsible for the reactivity trends observed in plasma-assisted NH 3 synthesis.

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

Controlling Amphiphilic Polymer Folding beyond the Primary Structure with Protein-Mimetic Di(Phenylalanine)

While methods for polymer synthesis have proliferated, their functionality pales in comparison to natural biopolymers–strategies are limited for building the intricate network of noncovalent interactions necessary to elicit complex, protein-like functions. Using a bioinspired di(phenylalanine) acrylamide (FF) monomer, we explored the impact of various noncovalent interactions in generating ordered assembled structures. Amphiphilic copolymers were synthesized that exhibit β-sheet-like local structure upon collapsing into single-chain assemblies in aqueous environments. Here, the systematic analysis of a series of amphiphilic copolymers illustrated that the global collapse is primarily driven by hydrophobic forces. Hydrogen-bonding and aromatic interactions stabilize local structure, as β-sheet-like interactions were identified via circular dichroism and thioflavin T fluorescence. Similar analysis of phenylalanine (F) and alanine-phenylalanine acrylamide (AF) copolymers found that distancing the aromatic residue from the polymer backbone is sufficient to induce β-sheet-like local structure akin to the FF copolymers; however, the interactions between AF subunits are less stable than those formed by FF. Further, hydrogen-bond donating hydrophilic monomers disrupt internal structure formed by FF within collapsed assemblies. Collectively, these results illuminate design principles for the facile incorporation of multiple facets of protein-mimetic, higher-order structure within folded synthetic polymers.

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

Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal–organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr 6 -MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet–visible–near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. As a result, this work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Most photochemistry occurs in the regime of weak light–matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light–matter interactions between an optical field and multiple molecules lead to collective hybrid light–matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. Here, the effect of strong light–matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light–matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

Cavities↗
DOE OSTI2025

Control Mechanisms for Self‐Sealing in Activated Clay‐Rich Faults Through Controlled Hydraulic Injection Experiment

Abstract In a high‐pressure injection fault activation experiment conducted at the Mont Terri underground research laboratory in Switzerland, the transmissivity of the Opalinus Clay fault significantly increased due to opening and shearing. The fluid injection, spanning a few hours, generated a 10 m radius fault activation patch. Subsequent pressure pulse tests conducted bi‐weekly for a year revealed the gradual return of fault transmissivity to its initial state. The study utilized fluid pressure decay analysis, optical fiber monitoring, continuous active source seismic measurements and borehole displacement sensors for measuring fault displacements. The fault zone exhibited a dilation of approximately 1.4 mm, associated with both normal and tangential movements during activation, resulting in a sudden transmissivity increase from 1 × 10 −12 to 3.2 × 10 −7 m 2 /s. Early post‐activation, transient compaction and the subsequent slow compaction were observed, transitioning to an extension regime. The pressure pulse tests demonstrated a rapid transmissivity drop by more than two orders of magnitude within the first 10 days, followed by a gradual and less pronounced decrease. Plastic shear and compaction dominated the transmissivity evolution until 70 days after injection ended, followed by a period where additional factors, such as clay mineral swelling, influenced the behavior. Extrapolation suggested a sealing process taking at least 50 years after the initial activation. Plain Language Summary A field‐scale fault activation experiment offers valuable insights into the elasto‐plastic processes governing the sealing of shale faults. The experiment reveals a rapid increase in the fault's transmissivity by approximately five orders of magnitude during activation. Subsequent observations show a gradual transmissivity decrease by about three orders of magnitude post‐activation, with slow long‐term plastic shear and compaction of the fault competing against secondary processes, notably clay mineral swelling. All conceptual models employed to interpret these field data converge on the estimation that the fault's return to its initial low transmissivity state would require a minimum of 50 years. Key Points High‐pressure injection fault activation experiment at the Mont Terri underground research laboratory Continuous transmissivity measurements record self‐sealing inside a clay‐rich fault zone Transmissivity undergoes a phase of domination by slow plastic compaction and shearing during the initial post‐activation period, with mineral swelling exerting its influence over the long term

Guglielmi, Yves↗
DOE OSTI2021

Dislocation interactions in olivine control postseismic creep of the upper mantle

Changes in stress applied to mantle rocks, such as those imposed by earthquakes, commonly induce a period of transient creep, which is often modelled based on stress transfer among slip systems due to grain interactions. However, recent experiments have demonstrated that the accumulation of stresses among dislocations is the dominant cause of strain hardening in olivine at temperatures ≤600 °C, raising the question of whether the same process contributes to transient creep at higher temperatures. Here, we demonstrate that olivine samples deformed at 25 °C or 1150–1250 °C both preserve stress heterogeneities of ~1 GPa that are imparted by dislocations and have correlation lengths of ~1 μm. The similar stress distributions formed at these different temperatures indicate that accumulation of stresses among dislocations also provides a contribution to transient creep at high temperatures. The results motivate a new generation of models that capture these intragranular processes and may refine predictions of evolving mantle viscosity over the earthquake cycle.

58 GEOSCIENCES↗
DOE OSTI2021

Spatio-temporal control of phenylpropanoid biosynthesis by inducible complementation of a cinnamate 4-hydroxylase mutant

Abstract Cinnamate 4-hydroxylase (C4H) is a cytochrome P450-dependent monooxygenase that catalyzes the second step of the general phenylpropanoid pathway. Arabidopsis reduced epidermal fluorescence 3 (ref3) mutants, which carry hypomorphic mutations in C4H, exhibit global alterations in phenylpropanoid biosynthesis and have developmental abnormalities including dwarfing. Here we report the characterization of a conditional Arabidopsis C4H line (ref3-2pOpC4H), in which wild-type C4H is expressed in the ref3-2 background. Expression of C4H in plants with well-developed primary inflorescence stems resulted in restoration of fertility and the production of substantial amounts of lignin, revealing that the developmental window for lignification is remarkably plastic. Following induction of C4H expression in ref3-2pOpC4H, we observed rapid and significant reductions in the levels of numerous metabolites, including several benzoyl and cinnamoyl esters and amino acid conjugates. These atypical conjugates were quickly replaced with their sinapoylated equivalents, suggesting that phenolic esters are subjected to substantial amounts of turnover in wild-type plants. Furthermore, using localized application of dexamethasone to ref3-2pOpC4H, we show that phenylpropanoids are not transported appreciably from their site of synthesis. Finally, we identified a defective Casparian strip diffusion barrier in the ref3-2 mutant root endodermis, which is restored by induction of C4H expression.

Plant Sciences↗
DOE OSTI2022

Transcription Factors Controlling the Rhizobium–Legume Symbiosis: Integrating Infection, Organogenesis and the Abiotic Environment

Abstract Legume roots engage in a symbiotic relationship with rhizobia, leading to the development of nitrogen-fixing nodules. Nodule development is a sophisticated process and is under the tight regulation of the plant. The symbiosis initiates with a signal exchange between the two partners, followed by the development of a new organ colonized by rhizobia. Over two decades of study have shed light on the transcriptional regulation of rhizobium–legume symbiosis. A large number of transcription factors (TFs) have been implicated in one or more stages of this symbiosis. Legumes must monitor nodule development amidst a dynamic physical environment. Some environmental factors are conducive to nodulation, whereas others are stressful. The modulation of rhizobium–legume symbiosis by the abiotic environment adds another layer of complexity and is also transcriptionally regulated. Several symbiotic TFs act as integrators between symbiosis and the response to the abiotic environment. In this review, we trace the role of various TFs involved in rhizobium–legume symbiosis along its developmental route and highlight the ones that also act as communicators between this symbiosis and the response to the abiotic environment. Finally, we discuss contemporary approaches to study TF-target interactions in plants and probe their potential utility in the field of rhizobium–legume symbiosis.

Cell Biology↗
DOE OSTI2024

Towards rational control of seed oil composition: dissecting cellular organization and flux control of lipid metabolism

Plant lipids represent a fascinating field of scientific study, in part due to a stark dichotomy in the limited fatty acid (FA) composition of cellular membrane lipids vs the huge diversity of FAs that can accumulate in triacylglycerols (TAGs), the main component of seed storage oils. With few exceptions, the strict chemical, structural, and biophysical roles imposed on membrane lipids since the dawn of life have constrained their FA composition to predominantly lengths of 16–18 carbons and containing 0–3 methylene-interrupted carbon-carbon double bonds in cis-configuration. However, over 450 “unusual” FA structures can be found in seed oils of different plants, and we are just beginning to understand the metabolic mechanisms required to produce and maintain this dichotomy. Here we review the current state of plant lipid research, specifically addressing the knowledge gaps in membrane and storage lipid synthesis from 3 angles: pathway fluxes including newly discovered TAG remodeling, key acyltransferase substrate selectivities, and the possible roles of “metabolons.”

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Nonaffine Strains Control Ductility of Metallic Glasses

The origin of limited plasticity in metallic glasses is elusive, with no apparent link to their atomic structure. In this study, we propose that the response of the glassy structure to applied stress, not the original structure itself, provides a gauge to predict the degree of plasticity. We carried out high-energy x-ray diffraction on various bulk metallic glasses (BMGs) under uniaxial compression within the elastic limit and evaluated the anisotropic pair distribution function. We show that the extent of local deviation from the affine (uniform) deformation in the elastic regime is strongly correlated with the plastic behavior of BMGs beyond yield, across chemical compositions and sample history. The results suggest that the propensity for collective local atomic rearrangements under stress promotes plasticity.

3-dimensional systems↗