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At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
NASA NTRS2020

Characterization of Cosmic Grain Analogs Formed at Low Temperature from Small Hydrocarbon Precursors in the NASA Ames COSmIC Facility

Here, we present the results of the first solid-phase ex situ analysis of cosmic grain analogs produced at low temperature (<200 K) in the NASA Ames COsmic SImulation Chamber (COSmIC) from small hydrocarbon precursors, methane (CH4) and acetylene (C2H2), seeded in an argon supersonic jet expansion and submitted to a plasma discharge. The plasma-induced chemical reactions, initiated between the precursor molecules and their atomic and molecular fragments, radicals and ions, produce larger molecules and eventually solid particles that are collected in situ under controlled conditions. Scanning electron microscopy (SEM) imaging was used to provide insight on the morphology and growth structure of the grains produced in COSmIC, and to investigate how the precursors used to produce the grains affect these parameters. This SEM study has shown that under identical experimental conditions with fixed physical and chemical parameters (precursor density, temperature, energy, and reaction time), heavier precursors in the initial mixture produce larger grains and in larger quantity, most likely as a result of a more complex chemistry: most of the grains produced in the Ar/CH4 (95:5) gas mixture ranged from 15 to 385 nm in diameter with an average density of 2.1 grains per sq.μm, while the grains produced in the Ar/C2H2 (95:5) gas mixture ranged from 40 to 650 nm with a density of 3.5 grains per sq.μm. Changes in the morphology were also observed, with grains produced from acetylene (C2H2) precursors tending to be more spherical than grains produced from methane (CH4) precursors. This change in morphology could be associated with different stages of growth formation at low temperature from a more "planar" growth at first, followed by coagulation into more spherical particles. This study demonstrates that the COSmIC experimental setup can be used to investigate carbon grain formation from small gas-phase molecular precursors at low temperature (<200 K), i.e., under a temperature regime that is representative of the dust condensation zone and outer region of circumstellar envelopes.

Ella Sciamma-O'Brien↗
DOE OSTI2021

Control of Catalyst Isomers Using an N -Phenyl-Substituted RN(CH 2 CH 2 P i Pr 2 ) 2 Pincer Ligand in CO 2 Hydrogenation and Formic Acid Dehydrogenation

A novel pincer ligand, i Pr PN Ph P [PhN- (CH 2 CH 2 P i Pr 2 ) 2 ], which is an analogue of the versatile MACHO ligand, iPr PN H P [HN(CH 2 CH 2 P i Pr 2 ) 2 ], was synthesized and characterized. The ligand was coordinated to ruthenium, and a series of hydride-containing complexes were isolated and characterized by NMR and IR spectroscopies, as well as X-ray diffraction. Comparisons to previously published analogues ligated by iPr PN H P and iPr PN Me P [CH 3 N(CH 2 CH 2 P i Pr 2 ) 2 ] illustrate that there are large changes in the coordination chemistry that occur when the nitrogen substituent of the pincer ligand is altered. For example, ruthenium hydrides supported by the iPr PN Ph P ligand always form the syn isomer (where syn/anti refer to the relative orientation of the group on nitrogen and the hydride ligand on ruthenium), whereas complexes supported by iPr PN H P form the anti isomer and complexes supported by iPr PN Me P form a mixture of syn and anti isomers. We evaluated the impact of the nitrogen substituent of the pincer ligand in catalysis by comparing a series of iPr PN R P (R = H, Me, Ph)-ligated ruthenium hydride complexes as catalysts for formic acid dehydrogenation and carbon dioxide (CO 2 ) hydrogenation to formate. The iPr PN Ph P-ligated species is the most active for formic acid dehydrogenation, and mechanistic studies suggest that this is likely because there are kinetic advantages for catalysts that operate via the syn isomer. In CO 2 hydrogenation, the iPr PN Ph P-ligated species is again the most active under our optimal conditions, and we report some of the highest turnover frequencies for homogeneous catalysts. Experimental and theoretical insights into the turnover-limiting step of catalysis provide a basis for the observed trends in catalytic activity. Additionally, the stability of our complexes enabled us to detect a previously unobserved autocatalytic effect involving the base that is added to drive the reaction. Overall, by modifying the nitrogen substituent on the MACHO ligand, we have developed highly active catalysts for formic acid dehydrogenation and CO 2 hydrogenation and also provided a framework for future catalyst development.

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

EF-Hand Battle Royale: Hetero-ion Complexation in Lanmodulin

The lanmodulin (LanM) protein has emerged as an effective means for rare earth element (REE) extraction and separation from complex feedstocks without the use of organic solvents. Whereas the binding of LanM to individual REEs has been well characterized, little is known about the thermodynamics of mixed metal binding complexes (i.e., heterogeneous ion complexes), which limits the ability to accurately predict separation performance for a given metal ion mixture. In this paper, we employ the law of mass action to establish a theory of perfect cooperativity for LanM-REE complexation at the two highest-affinity binding sites. The theory is then used to derive an equation that explains the nonintuitive REE binding behavior of LanM, where separation factors for binary pairs of ions vary widely based on the ratio of ions in the aqueous phase, a phenomenon that is distinct from single-ion-binding chemical chelators. We then experimentally validate this theory and perform the first quantitative characterization of LanM complexation with heterogeneous ion pairs using resin-immobilized LanM. Importantly, the resulting homogeneous and heterogeneous constants enable accurate prediction of the equilibrium state of LanM in the presence of mixtures of up to 10 REEs, confirming that the perfect cooperativity model is an accurate mechanistic description of REE complexation by LanM. We further employ the model to simulate separation performance over a range of homogeneous and heterogeneous binding constants, revealing important insights into how mixed binding differentially impacts REE separations based on the relative positioning of the ion pairs within the lanthanide series. In addition to informing REE separation process optimization, these results provide mathematical and experimental insight into competition dynamics in other ubiquitous and medically relevant, cooperative binding proteins, such as calmodulin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Unraveling design principles of protein landscapes in photosynthetic membranes in plant chloroplasts

The supramolecular organization of proteins within photosynthetic membranes is crucial for energy conversion in plants. Here, we introduce an analytical and computational pipeline that integrates high-resolution cryo–scanning electron microscopy, biochemical quantification, advanced Monte Carlo computer simulations, and statistical methods to elucidate the elusive protein landscapes of grana membranes in intact Arabidopsis leaves. Our integrated analysis challenges the prevailing view that particles on the exoplasmic fracture faces in freeze-fracture samples represent photosystem II exclusively. Instead, these particles also include cytochrome b 6 f complexes. Furthermore, our steric clash analysis demonstrates that stacked membranes contain a mixture of larger PSII supercomplexes (C 2 S 2 M 2 and C 2 S 2 ) in addition to a smaller complex (C 2 ). This suggests that in vivo PSII supercomplexes exist in an equilibrium distribution of differing sizes. Furthermore, we discovered that, although size exclusion effects govern the global protein arrangement, local packing exhibits orientational order indicative of lateral attractive protein-protein interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

Viscosity of multicomponent partially ionized gas mixtures

An approximate method is proposed for predicting the viscosity of partially ionized gas mixtures. This technique expresses the viscosity of a mixture in terms of the viscosities of the individual pure components, is simple in form, and does not require large computer run times or storage. Thus, the technique is suitable for use with complex flowfields and heat-transfer calculations. Results for gas mixtures which are representative of the atmospheres of Jupiter, Earth, and Venus, are presented and it is shown that the results compare favorably with detailed kinetic-theory analyses.

Armaly, B. F.↗
NASA NTRS1981

Thermal conductivity of partially ionized gas mixtures

A method is proposed for predicting the translational component of the thermal conductivity of partially ionized gas mixtures. It is approximate but simple in form and offers a significant improvement over commonly utilized approximations. It does not require large computer run times nor storage, thus it is suitable for use with complex flow fields and heat transfer calculations. Results for gas mixtures which are representative of the atmosphere of Jupiter, Earth, and Venus are presented and they compare favorably with results from detailed kinetic theory analyses.

Armaly, B. F.↗
DOE OSTI2025

Ion Clusters in Multicomponent Solutions Determined from X-ray PDF and SAXS Analysis: The NaNO 2 –NaOH–H 2 O System

Here, this study explores ion cluster formation in the NaNO 2 –NaOH–H 2 O system to understand how ion cluster formation is influenced by the composition in multicomponent mixtures. X-ray pair distribution function (PDF) and small-angle X-ray scattering (SAXS) identified complex ion clusters in concentrated NaNO 2 and NaOH solutions as well as their mixtures. PDF analysis showed that the Na–O distance depended primarily on total Na + concentrations rather than anion composition, whereas the nitrite-water oxygen distance stayed the same regardless of concentration or composition. This result indicates that the nitrite ion hydration was relatively independent of composition. SAXS confirms local fluctuations and coherent clusters with notable size differences between NaOH and NaNO 2 solutions. SAXS analysis of mixed solutions shows that their clusters are an average of the individual solutions, indicating mixed clusters.

Reynolds, Jacob G. [Central Plateau Cleanup Compan↗
DOE OSTI2021

Effects of non-thermal termolecular chemistry on detonation development in hydrogen (H2) / methane (CH4) - air mixtures

In combustion simulations, it is usually assumed that highly-energized collision complexes (either radical or stable species) formed in exothermic reactions are always under thermal equilibrium as they evolve through competing networks of reactions. However, in practical flames, non-trivial amounts of reactive radicals such as H, O and OH are present apart from O2. As a result, collisions of these reactive species with the energized collision complexes have been shown in recent studies to induce non-thermal reactivity. These studies have also demonstrated that such non-thermal reactions can be suitably represented in macroscopic kinetics models as chemically termolecular reactions. The present work was focused on identifying and quantifying the effects of including such reactions on the evolution of an initial deflagration front to a developing detonation in H2/CH4-air mixtures under boosted internal combustion (IC) engine conditions. Specifically, fully resolved simulations, with and without non-thermal reactivity, were performed for a constant volume reactor containing stoichiometric H2/CH4-air mixture. It was found that inclusion of termolecular chemistry resulted in a delayed onset of end-gas auto-ignition. Concurrently, the developing detonation intensity was observed to be significantly higher. Chemical explosive mode analysis (CEMA) was performed to identify the dominant species/reactions responsible for the observed variation in the results.

Detonation↗
DOE OSTI2023

Well-Defined Iron Sites in Crystalline Carbon Nitride

Carbon nitride materials can be hosts for transition metal sites, but Mössbauer studies on iron complexes in carbon nitrides have always shown a mixture of environments and oxidation states. Here we describe the synthesis and characterization of a crystalline carbon nitride with stoichiometric iron sites that all have the same environment. The material (formula C 6 N 9 H 2 Fe 0.4 Li 1.2 Cl, abbreviated PTI/FeCl 2 ) is derived from reacting poly(triazine imide)·LiCl (PTI/LiCl) with a low-melting FeCl 2 /KCl flux, followed by anaerobic rinsing with methanol. X-ray diffraction, X-ray absorption and Mössbauer spectroscopies, and SQUID magnetometry indicate that there are tetrahedral high-spin iron(II) sites throughout the material, all having the same geometry. As a result, the material is active for electrocatalytic nitrate reduction to ammonia, with a production rate of ca. 0.1 mmol cm –2 h –1 and Faradaic efficiency of ca. 80% at −0.80 V vs RHE.

Anions↗
DOE OSTI2020

Fast and Universal Kohn-Sham Density Functional Theory Algorithm for Warm Dense Matter to Hot Dense Plasma

Understanding many processes, e.g., fusion experiments, planetary interiors, and dwarf stars, depends strongly on microscopic physics modeling of warm dense matter and hot dense plasma. This complex state of matter consists of a transient mixture of degenerate and nearly free electrons, molecules, and ions. This regime challenges both experiment and analytical modeling, necessitating predictive ab initio atomistic computation, typically based on quantum mechanical Kohn-Sham density functional theory (KS-DFT). However, cubic computational scaling with temperature and system size prohibits the use of DFT through much of the warm dense matter regime. A recently developed stochastic approach to KS-DFT can be used at high temperatures, with the exact same accuracy as the deterministic approach, but the stochastic error can converge slowly and it remains expensive for intermediate temperatures (< 50 eV). Here we have developed a universal mixed stochastic-deterministic algorithm for DFT at any temperature. This approach leverages the physics of KS-DFT to seamlessly integrate the best aspects of these different approaches. We demonstrate that this method significantly accelerated self-consistent field calculations for temperatures from 3 to 50 eV, while producing stable molecular dynamics and accurate diffusion coefficients.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Combustion-Pele: An Exascale Capability for Improving Engine Design

Combustion, the complex chemical reaction made possible by igniting a mixture of fuel and oxygen to produce heat and light, serves as the nation’s primary source of power generation and the linchpin of the transportation industry. For more than 100 years, internal combustion engines (ICEs) have been converting energy from the burning of fuel—gasoline, for example—into a mechanical process that makes vehicles move. Recently, ICEs have come under heavy scrutiny for their contribution to greenhouse gas emissions, yet combustion-based systems are projected to dominate the marketplace for decades. Exascale systems are helping researchers design new high-efficiency, low-emission combustion engines that operate at much lower temperatures to maintain the nation’s energy security and limit negative environmental impacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Source of the optical red-slope in iron-rich meteorites

The relationship between ordinary chondrites and S-type asteroids is an unresolved issue in meteorite science. S-type asteroids exhibit a positively red-sloped spectrum that is interpreted to indicate the presence of elemental iron on the surfaces. The characteristic red-sloped spectrum of iron-rich meteorites is produced by only the specular component of the reflectance. Complex metallic surfaces can be modeled as linear mixtures of specular and nonspecular components. It is the geometry of the metal on a surface and its interaction with surrounding material, rather than the absolute amount of metal, that determine the redness of resulting spectra. In order to distinguish between ordinary chondrite and differentiated parent bodies it is important to understand how regolith processes affect the nature and form of metal on asteroid surfaces.

Britt, Daniel T.↗
NASA NTRS1993

Comparison of numerical simulation and experimental data for steam-in-place sterilization

A complex problem involving convective flow of a binary mixture containing a condensable vapor and noncondensable gas in a partially enclosed chamber was modelled and results compared to transient experimental values. The finite element model successfully predicted transport processes in dead-ended tubes with inside diameters of 0.4 to 1.0 cm. When buoyancy driven convective flow was dominant, temperature and mixture compositions agreed with experimental data. Data from 0.4 cm tubes indicate diffusion to be the primary air removal method in small diameter tubes and the diffusivity value in the model to be too large.

Young, Jack H.↗
NASA NTRS2004

In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars

Sedimentary rocks at Eagle crater in Meridiani Planum are composed of fine-grained siliciclastic materials derived from weathering of basaltic rocks, sulfate minerals (including magnesium sulfate and jarosite) that constitute several tens of percent of the rock by weight, and hematite. Cross-stratification observed in rock outcrops indicates eolian and aqueous transport. Diagenetic features include hematite-rich concretions and crystal-mold vugs. We interpret the rocks to be a mixture of chemical and siliciclastic sediments with a complex diagenetic history. The environmental conditions that they record include episodic inundation by shallow surface water, evaporation, and desiccation. The geologic record at Meridiani Planum suggests that conditions were suitable for biological activity for a period of time in martian history.

Water↗
NASA NTRS2018

The SPECTRAL Ice Chamber: Application to Titan's Stratospheric Ice Clouds

An ice chamber for obtaining thin-film transmission spectra of Titan-relevant organic ices between 50 and 11,700 cm−1 (200–0.85 μm) is described in detail in this work. The ice chamber, called the SPECtroscopy of Titan-Related ice AnaLogs chamber, is located in the Spectroscopy for Planetary ICes Environments laboratory at NASA Goddard Space Flight Center. Organic vapors are typically deposited between 30 and 150 K via a variable leak valve onto a chemical vapor deposition diamond substrate, where condensation directly into the solid state occurs. Quantitative thin-film infrared transmission spectra of the given ice or ice mixture are then measured, from which optical constants (complex indices of refraction) are computed. These optical constants in turn provide the necessary input for interpreting radiative transfer analyses of Cassini’s Composite InfraRed Spectrometer observations of Titan’s organic stratospheric ice clouds to determine their chemical compositions, abundances, and vertical distributions as functions of Titan latitude and season.

Anderson, C. M.↗
NASA NTRS2018

The SPECTRAL Ice Chamber: Application to Titan's Stratospheric Ice Clouds

An ice chamber for obtaining thin-film transmission spectra of Titan-relevant organic ices between 50 and 11,700 cm(exp −1) (200–0.85 μm) is described in detail in this work. The ice chamber, called the SPECtroscopy of Titan-Related ice AnaLogs chamber, is located in the Spectroscopy for Planetary ICes Environments laboratory at NASA Goddard Space Flight Center. Organic vapors are typically deposited between 30 and 150 K via a variable leak valve onto a chemical vapor deposition diamond substrate, where condensation directly into the solid state occurs. Quantitative thin-film infrared transmission spectra of the given ice or ice mixture are then measured, from which optical constants (complex indices of refraction) are computed. These optical constants in turn provide the necessary input for interpreting radiative transfer analyses of Cassini’s Composite InfraRed Spectrometer observations of Titan’s organic stratospheric ice clouds to determine their chemical compositions, abundances, and vertical distributions as functions of Titan latitude and season.

C. M. Anderson↗
NASA NTRS2018

The SPECTRAL Ice Chamber: Application to Titan's Stratospheric Ice Clouds

An ice chamber for obtaining thin-film transmission spectra of Titan-relevant organic ices between 50 and 11,700 cm−1 (200 to 0.85 µm) is described in detail in this work. The ice chamber, called the SPECtroscopy of Titan-Related ice AnaLogs (SPECTRAL) chamber, is located in the Spectroscopy for Planetary ICes Environments (SPICE) laboratory at NASA Goddard Space Flight Center (GSFC). Organic vapors are typically deposited between 30 K and 150 K via a variable leak valve onto a chemical vapor deposition (CVD) diamond substrate, where condensation directly into the solid state occurs. Quantitative thin-film infrared transmission spectra of the given ice or ice mixture are then measured, from which optical constants (complex indices of refraction) are computed. These optical constants in turn provide the necessary input for interpreting radiative transfer analyses of Cassini’s Composite InfraRed Spectrometer (CIRS) observations of Titan’s organic stratospheric ice clouds to determine their chemical compositions, abundances, and vertical distributions as functions of Titan latitude and season.

C. M. Anderson↗
DOE OSTI2023

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz), 5-amino-tetrazole (5-NH 2 -HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl 3 ⋅ 7H 2 O, [C 2 mim] 3 [CeCl 6 ] ([C 2 mim] + =1-ethyl-2-methylimidazolium), and Ce(NO 3 ) 3 ⋅ 6H 2 O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH 2 -1,2,4-Triaz is structure directing via η 2 μ 2 κ 2 bridging, with the formation of the dinuclear complexes [Ce 2 Cl 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (H 2 O) 8 ]Cl 4 ⋅ 4H 2 O, [Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 (Cl) 6 ], and [4-NH 2 -1,2,4-HTriaz][Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 2 (μ 2 -NO 3 )(NO 3 ) 6 (H 2 O) 2 ]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ] ⋅ 7H 2 O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M 6 X 8 core, and the first reported Ce(III) hexanuclear complex of this type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗