Crystal structure of a thermophilic fungal cyanase and its implications on the catalytic mechanism for bioremediation
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99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “enhanced kinetics”
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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Radiation Tests of the Extravehicular Mobility Unit Space Suit for the International Space Station Using Energetic Protons
Measurements using silicon detectors to characterize the radiation transmitted through the EMU space suit and a human phantom have been performed using 155 and 250 MeV proton beams at LLUMC. The beams simulate radiation encountered in space, where trapped protons having kinetic energies on the order of 100 MeV are copious. Protons with 100 MeV kinetic energy and above can penetrate many centimeters of water or other light materials, so that astronauts exposed to such energetic particles will receive doses to their internal organs. This dose can be enhanced or reduced by shielding - either from the space suit or the self-shielding of the body - but minimization of the risk depends on details of the incident particle flux (in particular the energy spectrum) and on the dose responses of the various critical organs. Data were taken to characterize the beams and to calibrate the detectors using the beam in a treatment room at LLUPTF, in preparation for an experiment with the same beams incident on detectors placed in a human phantom within the EMU suit. Nuclear interactions of high-energy protons in various materials produce a small flux of highly ionizing, low-energy secondary radiation. Secondaries are of interest for their biological effects, since they cause doses and especially dose-equivalents to increase relative to the values expected simply from ionization energy loss along the Bragg curve. Because many secondaries have very short ranges, they are best measured in passive track detectors such as CR-39. The silicon detector data presented here are intended to supplement the CR-39 data in regions where silicon has greater sensitivity, in particular the portion of the LET spectrum below 5 keV/micron. The results obtained in this study suggest that optimizing the radiation shielding properties of space suits is a formidable task. The naive assumption that adding mass can reduce risk is not supported by the data, which show that reducing the dose delivered at or near the skin by low-energy particles may increase the dose delivered by energetic particles to points deeper in the body.
Zeitlin, C.↗
Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst
A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H 2 followed by O 2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate determining. Electronic structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from that involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H 2 and, alternatively, with D 2 on the cluster incorporating the dioxygen ligands, and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H 2 with D 2 to give HD. Here, we posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.
02 PETROLEUM↗
Long‐Range Confinement‐Driven Enrichment of Surface Oxygen‐Relevant Species Promotes C−C Electrocoupling in CO 2 Reduction
Abstract CO 2 reduction is a highly attractive route to transform CO 2 into useful feedstocks, of which C 2 products are more desired than C 1 , yet face high kinetic barriers of C−C electrocoupling. Here, the engineering of pore‐enabled local confinement reaction environments is reported for tuning the enrichment of surface‐adsorbed oxygen‐relevant species and the establishment of their pronounced benefits in promoting C−C coupling over oxide‐derived Cu‐based catalysts. A new approach of utilizing the microphase separation of a block copolymer is developed to fabricate bicontinuous mesoporous CuO nanofibers (CuO‐BPNF). The enhanced confinement from long‐range mesochannels enables the adsorption of OH ad /O ad on the Cu surface at a wide negative potential range of −0.7 – −1.3 V in CO 2 reduction, which cannot be achieved over conventional deficient and short‐range pores. Constant‐potential DFT calculations reveal that the surface‐bound oxygen species weakens *CO affinity with the Cu (111) surface and lowers the kinetic barriers for both *CO−CO dimerization and *CO hydrogenation to enable *CO−CHO coupling. Accordingly, a CO 2 ‐to‐C 2 Faradaic efficiency of 74.7% over CuO‐BPNF is shown, significantly larger than counterparts with conventional pores. This work offers a general design principle of confinement engineering to manage the adsorption of reactive species for steering reaction pathways in interfacial catalysis.
Chemistry↗
Effects of Gasoline Composition and Operating Parameters on the Response of End-Gas Autoignition to Nitric Oxide in a Lean-Burn DI-SI Engine
Lean operation of spark-ignition engines can lead to engine thermal efficiency gains and lower NOx emissions due to reduced combustion temperatures. Yet, lean operation could still face challenges in end-gas autoignition and knock generation due to higher intake pressures and trapped NO in the residual gas. Here, this study evaluates the impact of NO on end-gas autoignition for two gasoline fuels with similar octane rating but different composition: high cycloalkane fuel (HCA) and high olefin fuel (HO). Experiments were performed at stoichiometric and lean (λ = 2) conditions and at two engine speeds of 1400 rpm and 2000 rpm. Accompanying chemical kinetics simulations in CHEMKIN revealed that the mechanisms controlling the effect of NO on autoignition are similar λ = 2 and λ = 1, with NO + HO 2 = NO 2 + OH being the main pathway for enhancing reactivity by promoting low-temperature heat release (LTHR). The compositionally different fuels reacted differently to NO seeding and engine speed, and differences were augmented at λ = 2 compared to λ = 1 as the end-gas autoignition shifted to the low temperature regime. HO, which has inherent low temperature chemistry, was strongly impacted by engine speed at low NO seeding levels, with no noticeable peak of LTHR detected at 2000 rpm. On the other hand, LTHR of HCA was marginally affected by shortened residence time at higher engine speed as NO + HO 2 reaction was not greatly affected by shorter time scales, since HO 2 production was sustained even at 2000 rpm to support OH generation from NO + HO 2 . Contrary to HO, HCA exhibited greater sensitivity to NO seeding, as the increased OH production at higher NO concentrations offset the OH-quenching effect of cyclopentane, which accounts for 28.6% of HCA’s composition. Consequently, a sensitivity analysis revealed that fuels with weak inherent low-temperature chemistry, like HCA, are likely to be more sensitive to variations in NO concentration and charge temperature, whereas fuels with strong low temperature chemistry are more sensitive to variations in end-gas λ and intake pressure.
Energy↗
Undercooling and solidification behavior in the InSb-Sb system
Use of the droplet emulsion technique has been successful in studying the undercooling and crystallization behavior of Sb, InSb, and an InSb-Sb eutectic alloy. Both droplet size and imposed cooling rate were influential in controlling the extent of liquid undercooling. The droplet surface coating was of significant importance in determining the resultant solidification product structure through its effect on nucleation kinetics. The maximum undercooling for pure Sb was extended from 0.08 to 0.23 T sub m. While simple crushing techniques provided a dramatic increase in droplet undercooling over the bulk material, emulsification treatments both enhanced this undercooling and allowed successful formation of a metastable simple cubic Sb phase. This phase was stable to temperatures approaching the melting point. The simple cubic phase was detected in droplet samples processed using DTA, air and water quenching, and drop tube processing under a helium gas atmosphere. A deviation in the InSb parent ingot composition limited interpretation of the line compound results, however, emulsification techniques extended the undercooling of this material to 0.17 T sub L and provided a stable, protective surface coating for the droplets. Emulsification of the eutectic alloy was effective at producing various levels of undercooling from 0.1 to 0.2 T sub E. Microstructural examination revealed a normal-type eutectic structure in the undercooled droplets indicating that solidification occurred within the coupled zone and that this zone is somewhat symmetric about the eutectic composition.
Graves, J. A.↗
A theory for narrow-banded radio bursts at Uranus - MHD surface waves as an energy driver
A possible scenario for the generation of the narrow-banded radio bursts detected at Uranus by the Voyager 2 planetary radio astronomy experiment is described. In order to account for the emission burstiness which occurs on time scales of hundreds of milliseconds, it is proposed that ULF magnetic surface turbulence generated at the frontside magnetopause propagates down the open/closed field line boundary and mode-converts to kinetic Alfven waves (KAW) deep within the polar cusp. The oscillating KAW potentials then drive a transient electron stream that creates the bursty radio emission. To substantiate these ideas, Voyager 2 magnetometer measurements of enhanced ULF magnetic activity at the frontside magnetopause are shown. It is demonstrated analytically that such magnetic turbulence should mode-convert deep in the cusp at a radial distance of 3 RU.
Farrell, W. M.↗
Magnetohydrodynamics Accelerator Research Into Advanced Hypersonics (MARIAH)
This report documents the activities, results, conclusions and recommendations of the Magnetohydrodynamics Accelerator Research Into Advanced Hypersonics (MARIAH) Project in which the use of magnetohydrodynamics (MHD) technology is investigated for its applicability to augment hypersonic wind tunnels. The long range objective of this investigation is to advance the development of ground test facilities to support the development of hypervelocity flight vehicles. The MHD accelerator adds kinetic energy directly to the wind tunnel working fluid, thereby increasing its Mach number to hypervelocity levels. Several techniques for MHD augmentation, as well as other physical characteristics of the process are studied to enhance the overall performance of hypersonic wind tunnel design. Specific recommendations are presented to improve the effectiveness of ground test facilities. The work contained herein builds on nearly four decades of research and experimentation by the aeronautics ground test and evaluation community, both foreign and domestic.
Micheletti, David A.↗
Magnetohydrodynamics Accelerator Research into Advanced Hypersonics (MARIAH)
This report documents the activities, results, conclusions and recommendations of the Magnetohydrodynamics Accelerator Research Into Advanced Hypersonics (MARIAH) Project in which the use of magnetohydrodynamics (MHD) technology is investigated for its applicability to augment hypersonic wind tunnels. The long range objective of this investigation is to advance the development of ground test facilities to support the development of hypervelocity flight vehicles. The MHD accelerator adds kinetic energy directly to the wind tunnel working fluid, thereby increasing its Mach number to hypervelocity levels. Several techniques for MHD augmentation, as well as other physical characteristics of the process are studied to enhance the overall performance of hypersonic wind tunnel design. Specific recommendations are presented to improve the effectiveness of ground test facilities. The work contained herein builds on nearly four decades of research and experimentation by the aeronautics ground test and evaluation community, both foreign and domestic.
Baughman, Jack A.↗
Advanced Fusion Reactors for Space Propulsion and Power Systems
In recent years the methodology proposed for conversion of light elements into energy via fusion has made steady progress. Scientific studies and engineering efforts in advanced fusion systems designs have introduced some new concepts with unique aspects including consideration of Aneutronic fuels. The plant parameters for harnessing aneutronic fusion appear more exigent than those required for the conventional fusion fuel cycle. However aneutronic fusion propulsion plants for Space deployment will ultimately offer the possibility of enhanced performance from nuclear gain as compared to existing ionic engines as well as providing a clean solution to Planetary Protection considerations and requirements. Proton triggered 11Boron fuel (p- 11B) will produce abundant ion kinetic energy for In-Space vectored thrust. Thus energetic alpha particles "exhaust" momentum can be used directly to produce high ISP thrust and also offer possibility of power conversion into electricity. p- 11B is an advanced fusion plant fuel with well understood reaction kinematics but will require some new conceptual thinking as to the most effective implementation.
Chapman, John J.↗
Insight into premixed diethoxymethane flames: Laminar burning velocities, temperatures, and emissions behaviour
Diethoxymethane ((CH 3 CH 2 O) 2 CH 2 , DEM) is a promising carbon-neutral fuel. DEM is a diether or acetal with a molecular structure similar to oxymethylene ethers (CH 3 O–(CH 2 O)n–CH 3 , OME n ). Thus, DEM can be expected to have a similar combustion behavior to OMEs, reducing harmful emissions such as NO x and particulate matter (PM) in internal combustion engines. From both experimental and kinetic modeling, fundamental studies on DEM are scarce in the literature. More studies are required to gain a detailed insight into the oxidation kinetics of DEM. Laminar burning velocity (LBV) is a critical property that allows a detailed assessment of the potential application of DEM in combustion devices. Unfortunately, the literature on the LBV of DEM is limited. Therefore, in this study we have investigated the LBV of DEM using two reactors for the first time, namely a heat flux burner and a combustion chamber. The experimental data is reported for equivalence ratio between 0.7 and 1.7, initial temperatures of 368–423 K, and initial pressure of 1–5 bar. In addition, we developed a detailed kinetic model extending our recent work of Shrestha et al. (Combust. Flame. 246 (2022) 112,426) to characterize the combustion behavior of DEM utilizing the new experimental data from this work and the literature data. Our model performs remarkably well in capturing the newly measured LBV experimental data over various experimental conditions. We found that DEM and dimethoxy methane (DMM) have similar values of LBVs (within ±1.5 cm/s) for a given condition, which indicates that intermediate chemistry governs the flame chemistry. Despite DEM being a larger molecule that is expected to have slightly lower LBVs than DMM, its effect on the measured values of LBVs is negligible. Finally, we experimentally measured NO x formation in DEM flame for the first time. The stochiometric flame has the highest NO x formation. The proposed model predicted the equivalence ratio dependence of NO x nicely. However, it overestimates the NO x formation for stoichiometric DEM/air mixtures by ~30 %. The model suggests that the thermal NO formation route is favored at lean and stochiometric conditions. In contrast, the prompt NO formation route is enhanced for rich mixtures.
10 SYNTHETIC FUELS↗
Spin alignment of vector mesons by glasma fields
We explain how spin alignment of vector mesons can be induced by background fields, such as electromagnetic fields or soft gluon fields. Our study is based on the quantum kinetic theory of spinning quarks and antiquarks and incorporates the relaxation of the dynamically generated spin polarization. The spin density matrix of vector mesons is obtained by quark coalescence via the Wigner function and kinetic equation. Our approach predicts a local spin correlation that is distinct from the nonlocal expressions previously obtained in phenomenological derivations. We estimate the magnitude of such local correlations in the glasma model of the preequilibrium phase of relativistic heavy ion collisions. It is found that the resulting spin alignment could be greatly enhanced and may be comparable to the experimental measurement in order of magnitude. We further propose new phenomenological scenarios to qualitatively explain the transverse-momentum and centrality dependence of spin alignment in a self-consistent framework.
79 ASTRONOMY AND ASTROPHYSICS↗
Stabilization of a nanoporous NiCu dilute alloy catalyst for non-oxidative ethanol dehydrogenation
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99 GENERAL AND MISCELLANEOUS↗
Enhanced steam oxidation resistance of uranium nitride nuclear fuel pellets
Here, the steam oxidation resistance of UN and UN-(20 vol%)ZrN fuel pellets is evaluated to enhance understanding of steam corrosion mechanisms in advanced nuclear fuel materials. In situ neutron diffraction shows the modified UN fuel pellets form a (U 0.77 ,Zr 0.23 )N solid-solution and the sole crystalline oxidation product detected in bulk is (U 0.77 ,Zr 0.23 )O 2 . U 2 N 3 is not detected in significant quantities during the steam oxidation of UN or (U 0.77 ,Zr 0.23 )N and stable lattice parameters show that hydriding does not take place. Steam oxidation rates, obtained via sequential Rietveld refinement show how (U 0.77 ,Zr 0.23 )N has a higher activation energy (79 ± 1 kJmol -1 vs. 50 ± 5 kJmol -1 ), higher onset temperature (430 °C vs. 400 °C) and slower reaction rates for steam oxidation up to 616 °C, than pure UN. Throughout, both UN and (U 0.77 ,Zr 0.23 )N exhibit linear (non-protective) oxidation kinetics, signifying that degradation of the fuel pellets is caused by the evolution of gaseous products at the interface followed by oxide scale spallation. This quantitative and mechanistic understanding of material degradation enables better defined operating regimes and points towards (U,Zr)N solid solutions as a promising strategy for the design of advanced nuclear fuel materials with enhanced steam corrosion resistance.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Kinetics, Ca2+ dependence, and biophysical properties of integrin-mediated mechanical modulation of transmitter release from frog motor nerve terminals
Neurotransmitter release from frog motor nerve terminals is strongly modulated by change in muscle length. Over the physiological range, there is an approximately 10% increase in spontaneous and evoked release per 1% muscle stretch. Because many muscle fibers do not receive suprathreshold synaptic inputs at rest length, this stretch-induced enhancement of release constitutes a strong peripheral amplifier of the spinal stretch reflex. The stretch modulation of release is inhibited by peptides that block integrin binding of natural ligands. The modulation varies linearly with length, with a delay of no more than approximately 1-2 msec and is maintained constant at the new length. Moreover, the stretch modulation persists in a zero Ca2+ Ringer and, hence, is not dependent on Ca2+ influx through stretch activated channels. Eliminating transmembrane Ca2+ gradients and buffering intraterminal Ca2+ to approximately normal resting levels does not eliminate the modulation, suggesting that it is not the result of release of Ca2+ from internal stores. Finally, changes in temperature have no detectable effect on the kinetics of stretch-induced changes in endplate potential (EPP) amplitude or miniature EPP (mEPP) frequency. We conclude, therefore, that stretch does not act via second messenger pathways or a chemical modification of molecules involved in the release pathway. Instead, there is direct mechanical modulation of release. We postulate that tension on integrins in the presynaptic membrane is transduced mechanically into changes in the position or conformation of one or more molecules involved in neurotransmitter release, altering sensitivity to Ca2+ or the equilibrium for a critical reaction leading to vesicle fusion.
Non-NASA Center↗
Water-Pillared Sodium Vanadium Bronze Nanowires for Enhanced Rechargeable Magnesium Ion Storage
Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium-ion batteries (MIBs) have more feasibility for large-scale energy storage compared to lithium-ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water-pillared sodium vanadium bronze nanowires (Na 2 V 6 O 16 ·1.63H 2 O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg 2+ diffusion. It exhibits high specific capacity of 175 mAh g -1 , long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g -1 , the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long-term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode material for low-cost and safe MIBs.
36 MATERIALS SCIENCE↗
Chemical trends favoring interstitial cluster formation in bcc high-entropy alloys from first-principles calculations
Achieving high strength and ductility is a common goal in structural alloy design. Body-centered cubic high-entropy alloys (HEAs) commonly highlight the conflict between these properties, with stronger alloys being brittle and vice versa. Recent reports suggest interstitial solutes can be used to overcome this trade-off, in some cases providing both strength and ductility enhancements. This effect has been correlated with interstitial cluster formation, although the conditions favoring their formation remain incompletely understood. Using first-principles calculations of solution energies and diffusivities, we provide insights into thermodynamic and kinetic factors favoring interstitial solute clusters. Among C, N and O solutes, O interstitials display most desirable diffusion kinetics. Further, the results highlight the importance of local composition fluctuations in the HEAs to enable the formation of clusters of appreciable size. The results are explained in terms of bonding and distortion trends across solutes and HEA compositions to provide guidelines for alloy design.
Borges, Pedro P P O↗
Ruthenium supported on silicate and aluminosilicate mesoporous materials applied to selective sugar hydrogenation: Xylose to xylitol
A series of ruthenium-based catalysts supported on a set of silicate and aluminosilicate mesoporous molecular sieves was synthesized and tested in xylose hydrogenation. The materials were characterized in terms of morphology, textural properties, acidity, as well as ruthenium loading, dispersion, and oxidation state. In general, the aluminosilicates-based catalysts displayed a higher activity compared to their respective silicate supports, which can be ascribed to a higher Ru content and dispersion, enhanced by a higher acidity. The most active synthesized catalyst (Ru/Al-MCM-4) displayed an improved performance compared to a commercial Ru/C catalyst due to a better xylitol selectivity. Two modelling approaches were implemented to describe the kinetic rate. The first model was based on the hypothesis that xylose molecules and hydrogen are adsorbed in different active sites on the catalyst surface, while the second model supposes the formation of an intermediate on the catalyst surface that reacts to form xylitol. Both models gave a very good description of the experimental data.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗