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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 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

High-spin non-heme iron–nitrosyls are of direct interest to both the chemical and biological communities as these species exhibit interesting chemical properties and act as direct models for enzymatic intermediates. The electronic ground state of the ferrous NO complexes, {Fe–NO} 7 , is best described as high-spin Fe III antiferromagnetically coupled to NO - , generating the spectroscopically observed S = 3/2 ground state. These species have been identified as catalytically relevant to a variety of NO-reducing enzymes such as bacterial nitric oxide reductase (NorBC) and flavo(rubredoxin) nitric oxide reductase (FNOR). Recently, the corresponding one-electron reduced {Fe–NO} 8 (nitroxyl) complexes have also been implicated as biologically significant species. In this review the available spectroscopic data for {Fe–NO} 7 and {Fe–NO} 8 mono- and dinuclear non-heme iron–nitrosyls are summarized, and the implications of these results with respect to the electronic structures and reactivities of these species, in particular towards NO reduction, are discussed.

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

Applying Anodic Stripping Voltammetry to Complex Wastewater Streams for Rapid Metal Detection (Final Report)

The overall objective of this project is the development of a lab-on-a-chip (LOC) electrochemical sensor capable of accurately measuring heavy metal (lead (Pb), cadmium (Cd), and arsenic (As)) concentrations in complex aqueous streams such as wastewater. The specific goals include: i) identify how heavy metal speciate and transform during the different stages of the wastewater treatment train, and explore pre-treatment methods that will de-complex heavy metals, making them available to ASV, ii) develop appropriate electrodes for ASV using organic/inorganic nanomaterials, and iii) integrate pre-treatment steps and specialized electrodes into an LOC sensor device capable of autonomously determining heavy metal concentrations in complex wastewater streams.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid

We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Impact of organic acids on extraction of rare earth elements: Mechanisms and optimization

Organic acids are increasingly recognized as an environmentally friendly and efficient selective leaching agent of critical minerals. However, their impact on subsequent extraction processes remains unclear. This study investigates the extraction behavior of rare earth elements (REEs), representative of critical minerals, in the presence of various organic acids, including citric acid, maleic acid, malonic acid, DL-malic acid, L(+)-tartaric acid, and L-ascorbic acid. The results show that organic acids slightly reduce the extraction of REEs but greatly increase the extraction of aluminum (Al³⁺), making it harder to separate REEs from other elements. To avoid this, it is best to keep organic acid concentrations as low as possible in practical applications. However, by optimizing extraction conditions, these negative effects can be minimized. Specifically, adjusting the contact time between solutions allows for efficient REE extraction while limiting unwanted aluminum extraction. Among the acids tested, malonic acid and L(+)-tartaric acid were found to be the most effective for selectively extracting REEs. Mechanistically, organic acids are likely to form complexes with REEs and D2EHPA during extraction, except for Y (III), offering practical guidelines for optimizing REE recovery. Beyond extraction, this study also highlights a way to recover organic acids by precipitating REEs from stripping solutions using oxalic acid, which adds both environmental and economic benefits. Furthermore, these findings provide useful insights for optimizing REE recovery and offer a reference for extracting other critical minerals from solutions containing organic acids.

D2EHPA↗
DOE OSTI2020

Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear Co IV –Dinitrate Complex

High-valent Fe IV =O intermediates with a terminal metal–oxo moiety are key oxidants in many enzymatic and synthetic C–H bond oxidation reactions. While generating stable metal–oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo–metal species of late transition metals have been recently described as strong oxidants that activate C–H bonds. In this work, we obtained an unprecedented mononuclear Co IV –dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt d z2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp 3 C–H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2–6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C–H bonds has yet to be observed for Co IV –O and Co III =O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species that is both structurally characterized by X-ray crystallography and capable of activating strong C–H bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Hydration of ferric chloride and nitrate in aqueous solutions: water-mediated ion pairing revealed by Raman spectroscopy

Iron is the most abundant transition metal in the earth's crust and is important for the proper functioning of many technological and natural processes. Despite the importance, a complete microscopic understanding of the hydration of ferric ions and water mediated ion pairing has not been realized. Hydrated Fe(III) is difficult to study due to the process of complexation to the anion and hydrolysis of the hydrating water molecules leading to a heterogeneous solution with diverse speciation. Here, ferric chloride and nitrate aqueous solutions are studied using polarized Raman spectroscopy as a function of concentration and referenced to their respective sodium salt or mineral acid. Perturbed water spectra (PWS) were generated using multivariate curve resolution-alternating least squares (MCR-ALS) to show the residual spectral response uniquely attributable to the hydration of ferric speciation. The hydrogen bonding network associated with the hydrating water molecules in ferric chloride solutions are found to be more similar to hydrochloric acid solutions, whereas in ferric nitrate solutions, the network behaves more similar to sodium nitrate, despite increased acidity. Thus, in the FeNO 3 and FeCl 3 solutions, ion pairing and coordination, respectively, are significantly influencing the hydration spectra signature. These results further reveal concentration dependent changes to the hydrogen bonding network, hydrating water symmetry, and changes to the relative abundance of solvent shared ion pairs that are governed primarily by the ferric salt identity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A directed-overflow and damage-control N -glycosidase in riboflavin biosynthesis

Plants and bacteria synthesize the essential human micronutrient riboflavin (vitamin B2) via the same multistep pathway. The early intermediates of this pathway are notoriously reactive, and may be overproduced in vivo because riboflavin biosynthesis enzymes lack feedback controls. Here we demonstrate disposal of riboflavin intermediates by COG3236 (DUF1768), a protein of previously unknown function that is fused to two different riboflavin pathway enzymes in plants and bacteria (RIBR and RibA, respectively). We present cheminformatic, biochemical, genetic, and genomic evidence to show that: (i) plant and bacterial COG3236 proteins cleave the N-glycosidic bond of the first two intermediates of riboflavin biosynthesis, yielding relatively innocuous products; (ii) certain COG3236 proteins are in a multienzyme riboflavin biosynthesis complex that gives them privileged access to riboflavin intermediates; and (iii) COG3236 action in Arabidopsis thaliana and Escherichia coli helps maintain flavin levels. We find COG3236 proteins thus illustrate two emerging principles in chemical biology: directed overflow metabolism, in which excess flux is diverted out of a pathway, and the pre-emption of damage from reactive metabolites.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

High pressure-induced distortion in face-centered cubic phase of thallium

The complex and unusual high-pressure phase transition of III-A (i.e. Al, Ga, and In) metals have been investigated in the last several decades because of their interesting periodic table position between the elements having metallic and covalent bonding. Here, our present first principles-based electronic structure calculations and experimental investigation have revealed the unusual distortion in face-centered cubic (f.c.c.) phase of the heavy element thallium (Tl) induced by the high pressure. We have predicted body-centered tetragonal (b.c.t) phase at 83 GPa using an evolutionary algorithm coupled with ab initio calculations, and this prediction has been confirmed with a slightly distorted parameter (2–√ × a-c)/c lowered by 1% using an angle-dispersive X-ray diffraction technique. The density functional theory (DFT)-based calculations suggest that s–p mixing states and the valence-core overlapping of 6s and 5d states play the most important roles for the phase transitions along the pathway h.c.p→f.c.c.→b.c.t.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Expression and Association of the Yersinia pestis Translocon Proteins, YopB and YopD, Are Facilitated by Nanolipoprotein Particles

Yersinia pestis enters host cells and evades host defenses, in part, through interactions between Yersinia pestis proteins and host membranes. One such interaction is through the type III secretion system, which uses a highly conserved and ordered complex for Yersinia pestis outer membrane effector protein translocation called the injectisome. The portion of the injectisome that interacts directly with host cell membranes is referred to as the translocon. The translocon is believed to form a pore allowing effector molecules to enter host cells. To facilitate mechanistic studies of the translocon, we have developed a cell-free approach for expressing translocon pore proteins as a complex supported in a bilayer membrane mimetic nano-scaffold known as a nanolipoprotein particle (NLP) Initial results show cell-free expression of Yersinia pestis outer membrane proteins YopB and YopD was enhanced in the presence of liposomes. However, these complexes tended to aggregate and precipitate. With the addition of co-expressed (NLP) forming components, the YopB and/or YopD complex was rendered soluble, increasing the yield of protein for biophysical studies. Biophysical methods such as Atomic Force Microscopy and Fluorescence Correlation Spectroscopy were used to confirm that the soluble YopB/D complex was associated with NLPs. An interaction between the YopB/D complex and NLP was validated by immunoprecipitation. The YopB/D translocon complex embedded in a NLP provides a platform for protein interaction studies between pathogen and host proteins. Ultimately, these studies will help elucidate the poorly understood mechanism which enables this pathogen to inject effector proteins into host cells, thus evading host defenses.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Membrane-organized Chemical Photoredox Systems

The key photoredox process in photosynthesis is the accumulation of oxidizing equivalents on a tetranuclear manganese cluster that then liberates electrons and protons from water and forms oxygen gas. Our primary goal in this project is to characterize inorganic systems that can perform this same water-splitting chemistry. One such species is the dinuclear ruthenium complex known as the blue dimer. Starting at the Ru(III,III) oxidation state, the blue dimer is oxidized up to a putative Ru(V,V) level prior to O-O bond formation. We employ electron paramagnetic resonance spectroscopy to characterize each step in this reaction cycle to gain insight into the molecular mechanism of water oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1976

The pollution reduction technology program for can-annular combustor engines - Description and results

Pollutant reduction and performance characteristics were determined for three successively more advanced combustor concepts. Program Element I consisted of minor modifications to the current production JT8D combustor and fuel system to evaluate means of improved fuel preparation and changes to the basic airflow distribution. Element II addressed versions of the two-staged Vorbix (vortex burning and mixing) combustor and represented a moderate increase in hardware complexity and difficulty of development. The concept selected for Element III employed vaporized fuel as a means of achieving minimum emission levels and represented the greatest difficulty of development and adaptation to the JT8D engine. Test results indicate that the Element I single-stage combustors were capable of dramatic improvement in idle pollutants. The multistage combustors evaluated in Program Elements II and III simultaneously reduced CO, THC and NOx emissions, but were unable to satisfy the current 1979 EPA standards.

Roberts, R.↗
NASA NTRS1995

Faint Object Camera imaging and spectroscopy of NGC 4151

We describe ultraviolet and optical imaging and spectroscopy within the central few arcseconds of the Seyfert galaxy NGC 4151, obtained with the Faint Object Camera on the Hubble Space Telescope. A narrowband image including (O III) lambda(5007) shows a bright nucleus centered on a complex biconical structure having apparent opening angle approximately 65 deg and axis at a position angle along 65 deg-245 deg; images in bands including Lyman-alpha and C IV lambda(1550) and in the optical continuum near 5500 A, show only the bright nucleus. In an off-nuclear optical long-slit spectrum we find a high and a low radial velocity component within the narrow emission lines. We identify the low-velocity component with the bright, extended, knotty structure within the cones, and the high-velocity component with more confined diffuse emission. Also present are strong continuum emission and broad Balmer emission line components, which we attribute to the extended point spread function arising from the intense nuclear emission. Adopting the geometry pointed out by Pedlar et al. (1993) to explain the observed misalignment of the radio jets and the main optical structure we model an ionizing radiation bicone, originating within a galactic disk, with apex at the active nucleus and axis centered on the extended radio jets. We confirm that through density bounding the gross spatial structure of the emission line region can be reproduced with a wide opening angle that includes the line of sight, consistent with the presence of a simple opaque torus allowing direct view of the nucleus. In particular, our modelling reproduces the observed decrease in position angle with distance from the nucleus, progressing initially from the direction of the extended radio jet, through our optical structure, and on to the extended narrow-line region. We explore the kinematics of the narrow-line low- and high-velocity components on the basis of our spectroscopy and adopted model structure.

Boksenberg, A.↗
NASA NTRSDate not supplied

Assessing the Radiative Impact of the 2019 – 2020 Australian Bushfires using Trajectory-Mapped CALIPSO Observations.

During the 2019/2020 fire season, Australian bushfires burned 46 million acres, killed 39 people and billions of animals, and became the costlier fire season in Australian history. Between the end of December and early January, a series of pyrocumulonimbus injected thick smoke layers in the upper troposphere and lower stratosphere which were observed over the Tasmanian Sea and New Zealand by the Ozone Mapping and Profiler Suite (OMPS) and the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO). The smoke plume crossed the tropopause and was further dispersed across the Eastern Pacific Ocean rising up to 30 km height after two weeks. . In this study, we use CALIPSO and the NASA Langley Trajectory Model (LaTM), driven by Modern-Era Retrospective analysis for Research and Application, Version 2 (MERRA-2) meteorological data, to track the dispersion of Australian fire smoke plumes in both the troposphere and the stratosphere. Trajectory mapping is used to re-construct the 3-dimension structure of the smoke plumes. Results are compared with independent observations from the Stratospheric Aerosol and Gas Experiment (SAGE) III on the International Space Station (ISS) to understand the complex transport of the plume into the stratosphere and its lifetime. Using trajectory maps, the impact of the Australian bushfires on the Earth’s radiative energy budget is assessed with the Clouds and the Earth’s Radiant Energy System (CERES).

Australian Bushfires↗
NASA NTRSDate not supplied

Assessing the Radiative Impact of the 2019 – 2020 Australian Bushfires using Trajectory-Mapped CALIPSO and SAGE III/ISS Observations.

During the 2019/2020 fire season, Australian bushfires burned 46 million acres, killed 39 people and billions of animals, and became the costlier fire season in Australian history. Between the end of December and early January, a series of pyrocumulonimbus injected thick smoke layers in the upper troposphere and lower stratosphere which were observed over the Tasmanian Sea and New Zealand by the Ozone Mapping and Profiler Suite (OMPS) and the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO). The smoke plume crossed the tropopause and was further dispersed across the Eastern Pacific Ocean rising up to 30 km height after two weeks. . In this study, we use CALIPSO and the NASA Langley Trajectory Model (LaTM), driven by Modern-Era Retrospective analysis for Research and Application, Version 2 (MERRA-2) meteorological data, to track the dispersion of Australian fire smoke plumes in both the troposphere and the stratosphere. Trajectory mapping is used to re-construct the 3-dimension structure of the smoke plumes. Results are compared with independent observations from the Stratospheric Aerosol and Gas Experiment (SAGE) III on the International Space Station (ISS) to understand the complex transport of the plume into the stratosphere and its lifetime. Using trajectory maps, the impact of the Australian bushfires on the Earth’s radiative energy budget is assessed with the Clouds and the Earth’s Radiant Energy System (CERES).

Australian bushfire↗
DOE OSTI2017

Mechanism of Ferric Oxalate Photolysis

Iron(III) oxalate, Fe 3+ (C 2 O 4 ) 3 3– , is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2 O and H 2 O up to 3 ns following photoexcitation. We find that intramolecular electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2 (aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Synthesis and structure of ruthenium complexes [Ph{sub 3}PCH{sub 2}C{sub 6}H{sub 4}F-4]{sub 2}[RuCl{sub 6}] and [Ph{sub 3}PCH{sub 2}C{sub 6}H{sub 4}F-4][trans-RuCl{sub 4}(dmso-S){sub 2}]

The reaction of (4-fluorobenzyl)triphenylphosphonium chloride with ruthenium(III) chloride hydrate in the presence of hydrochloric acid in dimethyl sulfoxide affords the complex [Ph{sub 3}PCH{sub 2}C{sub 6}H{sub 4}F-4]{sub 2}[RuCl{sub 6}]. In the absence of hydrochloric acid, the reaction gives the complex [Ph{sub 3}PCH{sub 2}C{sub 6}H{sub 4}F-4][trans-RuCl{sub 4}(dmso-S){sub 2}]. The structures of the complexes were studied by {sup 1}H, {sup 19}F, and {sup 31}P NMR spectroscopy and X-ray diffraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗