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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 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Protective effects and mechanisms of curcumin on podophyllotoxin toxicity in vitro and in vivo

Podophyllotoxin (POD) is a naturally occurring lignan with pronounced antineoplastic and antiviral properties. POD binds to tubulin and prevents the formation of mitotic spindle. Although cases of overdose or accidental ingestion are quite often, no specific therapy is currently available to treat the POD intoxication. In the current investigation, the protective effects and mechanisms of curcumin (CUR) on podophyllotoxin toxicity were evaluated in vitro and in vivo. The results showed that CUR could protect POD-induced cytotoxicity by recovering the G2/M arrest and decrease the changes of membrane potential and microtubule structure in Vero cells. A significant decrease of mortality rates was observed in Swiss mice treated by intragastrical administration of POD + CUR as compared with POD alone. The POD + CUR group also exhibited decreases in plasma transaminases, alkaline phosphatase, lactate dehydrogenase, plasma urea, creatinine and malondialdehyde level but elevated superoxide dismutase and glutathione levels as compared to the POD group. Histological examination of the liver and kidney demonstrated less morphological changes in the treatment of POD + CUR as compared with POD alone. The mechanism of the protective effects might be due to the competitive binding of CUR with POD in the same colchicines binding site as revealed by the tubulin polymerization assay and the molecular docking analysis, and the antioxidant activity against the oxidative stress induced by POD. In summary, both in vitro and in vivo data indicated the promising role of CUR as a protective agent against the POD poisoning. Highlights: ► A potential antidote to treat the podophyllotoxin (POD) intoxication is found. ► Curcumin showed promising effects against POD poisoning in vitro and in vivo. ► The mechanisms lie in the antioxidant activity and competitive binding with tubulin.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

The inhibitory and combinative mechanism of HZ08 with P-glycoprotein expressed on the membrane of Caco-2 cell line

Recently, the research and development of agents to reverse the phenomenon of multidrug resistance has been an attractive goal as well as a key approach to elevating the clinical survival of cancer patients. Although three generations of P-glycoprotein modulators have been identified, poor clearance and metabolism render these agents too toxic to be used in clinical application. HZ08, which has been under investigation for several years, shows a dramatic reversal effect with low cytotoxicity. For the first time, we aimed to describe the interaction between HZ08 and P-glycoprotein in Caco-2 cell line in which P-glycoprotein is overexpressed naturally. Cytotoxicity and multidrug resistance reversal assays, together with flow cytometry, fluorescence microscopy and siRNA interference as well as Caco-2 monolayer transport model were employed in this study to evaluate the interaction between HZ08 and P-glycoprotein. This study revealed that HZ08 was capable of reversing adriamycin resistance mediated by P-glycoprotein as a result of intracellular enhancement of adriamycin accumulation, which was found to be superior to verapamil. In addition, we confirmed that HZ08 suppressed the transport of Rhodamine123 in the Caco-2 monolayer model but had little effect on P-glycoprotein expression. The transport of HZ08 was diminished by P-glycoprotein inhibitors (verapamil and LY335979) and its accumulation was increased via siRNA targeting MDR1 in Caco-2 cells. Furthermore, considering the binding site of P-glycoprotein, verapamil performed as a competitive inhibitor with HZ08. In conclusion, as a P-glycoprotein substrate, HZ08 inhibited P-glycoprotein activity and may share the same binding site of verapamil to P-glycoprotein. - Highlights: • The cytotoxicity and reversing effect of HZ08 was measured in Caco-2 cell line. • HZ08 inhibited the transport of Rhodamine123 across Caco-2 cell monolayer. • The efflux ratio of HZ08 was dropped when combined with P-glycoprotein inhibitors. • The accumulation of HZ08 increased via gene interference targeting P-glycoprotein. • HZ08 competitively bound to P-glycoprotein under the presence of verapamil.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Potential transfer of neurotoxic amino acid β-N-methylamino-alanine (BMAA) from mother to infant during breast-feeding: Predictions from human cell lines

β-N-methylamino-alanine (BMAA) is a non-protein amino acid produced by cyanobacteria, diatoms and dinoflagellates. BMAA has potential to biomagnify in a terrestrial food chain, and to bioaccumulate in fish and shellfish. We have reported that administration of [{sup 14}C]L-BMAA to lactating mice and rats results in a mother to off-spring transfer via the milk. A preferential enantiomer-specific uptake of [{sup 14}C]L-BMAA has also been demonstrated in differentiated murine mammary epithelium HC11 cells. These findings, together with neurotoxic effects of BMAA demonstrated both in vitro and in vivo, highlight the need to determine whether such transfer could also occur in humans. Here, we used four cell lines of human origin to examine and compare the transport of the two BMAA enantiomers in vitro. The uptake patterns of [{sup 14}C]L- and [{sup 14}C]D-BMAA in the human mammary MCF7 cell line were in agreement with the results in murine HC11 cells, suggesting a potential secretion of BMAA into human breast milk. The permeability coefficients for both [{sup 14}C]L- and [{sup 14}C]D-BMAA over monolayers of human intestinal Caco2 cells supported an efficient absorption from the human intestine. As a final step, transport experiments confirmed that [{sup 14}C]L-and [{sup 14}C]D-BMAA can be taken up by human SHSY5Y neuroblastoma cells and even more efficiently by human U343 glioblastoma cells. In competition experiments with various amino acids, the ASCT2 specific inhibitor benzylserine was the most effective inhibitor of [{sup 14}C]L-BMAA uptake tested here. Altogether, our results suggest that BMAA can be transferred from an exposed mother, via the milk, to the brain of the nursed infant. - Highlights: • Transport of BMAA in human intestinal, mammary and CNS cell lines was examined. • The transport of L-BMAA over intestinal cell monolayers was unidirectional. • Enantiomer-selective uptake of L-BMAA in breast, neuron and glia cells was evident. • Competition experiments indicate that L-BMAA uptake involved several transporters. • A potential for mother to infant transfer of BMAA is proposed.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Evaluation of non-invasive biomonitoring of 2,4-Dichlorophenoxyacetic acid (2,4-D) in saliva

The objective of this study was to evaluate the potential for noninvasive biomonitoring of 2,4-dichlorophenoxyacetic acid (2,4-D) in saliva. Using an in vitro rat salivary gland epithelial cell (SGEC) system, a collection of experiments investigating chemical protein binding, temporal and directional transport, as well as competitive transport with para-aminohippuric acid (PAH), a substrate for renal organic anion transporters, was conducted to identify cellular transport parameters required to computationally model salivary transport of 2,4-D. Additionally, a physiological protein gradient was implemented to mimic physiologically relevant concentrations of protein in rat plasma and saliva, and under these conditions the transfer of 2,4-D was markedly slower, driven by increased protein binding (i.e. reduced free 2,4-D species available to cross salivary barrier). The rate of transfer was directly proportional to the amount of unbound 2,4-D and demonstrated no indication of active transport. An in vivo assessment of 2,4-D exposure in rats revealed a non-linear protein binding response in plasma, indicating saturated protein binding and increased levels of free 2,4-D species at higher doses. A strong correlation between concentrations in saliva and free unbound species in plasma was observed (Pearson correlation coefficient = 0.95). Saliva:plasma 2,4-D ratios measured in vivo (0.0079) were comparable over dose, but significantly different than ratios measured in vitro (physiological conditions) (0.034), possibly due to 2,4-D concentrations in saliva not being at equilibrium with 2,4-D concentrations in blood, as well as physiological features absent in in vitro settings (e.g. blood flow). We demonstrated that 2,4-D is consistently transported into saliva using both in vitro and in vivo models, making 2,4-D a potential candidate for human non-invasive salivary biomonitoring. Further work is needed to understand whether current sensor limits of detection are sufficient to measure occupationally relevant exposures.

Carver, Zana A.↗
DOE OSTI2019

Regulating TNCs: Should Uber and Lyft set their own rules?

We evaluate the impact of three proposed regulations of transportation network companies (TNCs) like Uber, Lyft and Didi: (1) A minimum wage for drivers, (2) a cap on the number of drivers or vehicles, and (3) a per-trip congestion tax. The impact is assessed using a queuing theoretic equilibrium model which incorporates the stochastic dynamics of the app-based ride-hailing matching platform, the ride prices and driver wages established by the platform, and the incentives of passengers and drivers. We show that a floor placed under driver earnings can push the ride-hailing platform to hire more drivers and offer more rides, at the same time that passengers enjoy faster rides and lower total cost, while platform rents are reduced. Contrary to standard competitive labor market theory, enforcing a minimum wage for drivers benefits both drivers and passengers, and promotes the efficiency of the entire system. This surprising outcome holds for almost all model parameters, and it occurs because the wage floor curbs TNC labor market power. In contrast to a wage floor, imposing a cap on the number of vehicles hurts drivers, because the platform reaps all the benefits of limiting supply. The congestion tax has the expected impact: fares increase, wages and platform revenue decrease. Here, we also construct variants of the model to briefly discuss platform subsidy, platform competition, and autonomous vehicles.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2013

Towards a coherent European approach for taxation of combustible waste

Highlights: • Current European waste taxes do not constitute a level playing field. • Integrating waste incineration in EU ETS avoids regional tax competition. • A differentiated incineration tax is a second-best instrument for NO{sub x} emissions. • A tax on landfilled incineration residues stimulates ash treatment. - Abstract: Although intra-European trade of combustible waste has grown strongly in the last decade, incineration and landfill taxes remain disparate within Europe. The paper proposes a more coherent taxation approach for Europe that is based on the principle of Pigovian taxation, i.e. the internalization of environmental damage costs. The approach aims to create a level playing field between European regions while reinforcing incentives for sustainable management of combustible waste. Three important policy recommendations emerge. First, integrating waste incineration into the European Emissions Trading System for greenhouse gases (EU ETS) reduces the risk of tax competition between regions. Second, because taxation of every single air pollutant from waste incineration is cumbersome, a differentiated waste incineration tax based on NO{sub x} emissions can serve as a second-best instrument. Finally, in order to strengthen incentives for ash treatment, a landfill tax should apply for landfilled incineration residues. An example illustrates the coherence of the policy recommendations for incineration technologies with diverse environmental effects.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Landfill reduction experience in The Netherlands

Highlights: • ‘Zero waste’ initiatives never consider risks, side effects or experience of achieved low levels of landfill. • This paper provides insight into what works and what not. • Where strong gradients in regulations and tax occur between countries, waste will find its way to landfills across borders. • Strong landfill reduction can create a fierce competition over the remaining waste to be landfilled resulting in losses. • At some point a public organisation should take responsibility for the operation of a ‘safety net’ in waste management. - Abstract: Modern waste legislation aims at resource efficiency and landfill reduction. This paper analyses more than 20 years of landfill reduction in the Netherlands. The combination of landfill regulations, landfill tax and landfill bans resulted in the desired landfill reduction, but also had negative effects. A fierce competition developed over the remaining waste to be landfilled. In 2013 the Dutch landfill industry generated €40 million of annual revenue, had €58 million annual costs and therefore incurred an annual loss of €18 million. It is not an attractive option to prematurely end business. There is a risk that Dutch landfill operators will not be able to fulfil the financial obligations for closure and aftercare. Contrary to the polluter pays principle the burden may end up with society. EU regulations prohibiting export of waste for disposal are in place. Strong differentials in landfill tax rate between nations have nevertheless resulted in transboundary shipment of waste and in non-compliance with the self-sufficiency and proximity principles. During the transformation from a disposal society to a recycling society, it is important to carefully plan required capacity and to guide the reorganisation of the landfill sector. At some point, it is no longer profitable to provide landfill services. It may be necessary for public organisations or the state to take responsibility for the continued operation of a ‘safety net’ in waste management. Regulations have created a financial incentive to pass on the burden of monitoring and controlling the impact of waste to future generations. To prevent this, it is necessary to revise regulations on aftercare and create incentives to actively stabilise landfills.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Inhibition of glycogen synthase kinase-3 enhances the differentiation and reduces the proliferation of adult human olfactory epithelium neural precursors

The olfactory epithelium (OE) contains neural precursor cells which can be easily harvested from a minimally invasive nasal biopsy, making them a valuable cell source to study human neural cell lineages in health and disease. Glycogen synthase kinase-3 (GSK-3) has been implicated in the etiology and treatment of neuropsychiatric disorders and also in the regulation of murine neural precursor cell fate in vitro and in vivo. In this study, we examined the impact of decreased GSK-3 activity on the fate of adult human OE neural precursors in vitro. GSK-3 inhibition was achieved using ATP-competitive (6-bromoindirubin-3'-oxime and CHIR99021) or substrate-competitive (TAT-eIF2B) inhibitors to eliminate potential confounding effects on cell fate due to off-target kinase inhibition. GSK-3 inhibitors decreased the number of neural precursor cells in OE cell cultures through a reduction in proliferation. Decreased proliferation was not associated with a reduction in cell survival but was accompanied by a reduction in nestin expression and a substantial increase in the expression of the neuronal differentiation markers MAP1B and neurofilament (NF-M) after 10 days in culture. Taken together, these results suggest that GSK-3 inhibition promotes the early stages of neuronal differentiation in cultures of adult human neural precursors and provide insights into the mechanisms by which alterations in GSK-3 signaling affect adult human neurogenesis, a cellular process strongly suspected to play a role in the etiology of neuropsychiatric disorders.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Transients following the loss of detonation confinement

We present a theory for the evolution of a one-dimensional, steady-state detonation reaction zone to a two-dimensional reaction zone, when the explosive experiences a sudden loss of side-on confinement as a boundary of the explosive is impulsively withdrawn. Our focus is on condensed-phase explosives, which we describe as having a constant adiabatic gamma equation of state and an irreversible, state-independent reaction rate. We consider two detonation models: (i) the instantaneous reaction heat release Chapman–Jouguet (CJ)-limit and (ii) the spatially resolved reaction heat-release Zel’dovich–von Neumann–Döring (ZND) model, in the limit where only a small fraction of the energy release is resolved (the SRHR-limit). Two competing rarefaction waves are generated by this loss of confinement: (i) a smooth wave coming off the full length of the withdrawn boundary and (ii) a singular fan spreading out from the point where the detonation shock and the withdrawn boundary meet. For the CJ-limit, in all cases the singular rarefaction fan eventually dominates the competition to control the steady-state behaviour. For the SRHR-limit, the spatially resolved heat release moderates this competition. When the withdrawal speed is fast, the rarefaction fan dominates; when the withdrawal speed is slower, the smooth rarefaction eventually dominates, although the flow features a fan at early times. By examining the mathematical properties of the steady two-dimensional fan-based solution, we set down a mechanism for this transition in behaviours.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Inactivation of Mandelate Racemase by 3-Hydroxypyruvate Reveals a Potential Mechanistic Link between Enzyme Superfamilies

Mandelate racemase (MR), a member of the enolase superfamily, catalyzes the Mg 2+ -dependent interconversion of the enantiomers of mandelate. Several α-keto acids are modest competitive inhibitors of MR [e.g., mesoxalate (K i = 1.8 ± 0.3 mM) and 3-fluoropyruvate (K i = 1.3 ± 0.1 mM)], but, surprisingly, 3-hydroxypyruvate (3-HP) is an irreversible, time-dependent inhibitor (k inact /K I = 83 ± 8 M –1 s –1 ). Protection from inactivation by the competitive inhibitor benzohydroxamate, trypsinolysis and electrospray ionization tandem mass spectrometry analyses, and X-ray crystallographic studies reveal that 3-HP undergoes Schiff-base formation with Lys 166 at the active site, followed by formation of an aldehyde/enol(ate) adduct. Such a reaction is unprecedented in the enolase superfamily and may be a relic of an activity possessed by a promiscuous progenitor enzyme. The ability of MR to form and deprotonate a Schiff-base intermediate furnishes a previously unrecognized mechanistic link to other α/β-barrel enzymes utilizing Schiff-base chemistry and is in accord with the sequence- and structure-based hypothesis that members of the metal-dependent enolase superfamily and the Schiff-base-forming N-acetylneuraminate lyase superfamily and aldolases share a common ancestor.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

The Antinociceptive Agent SBFI-26 Binds to Anandamide Transporters FABP5 and FABP7 at Two Different Sites

Human FABP5 and FABP7 are intracellular endocannabinoid transporters. SBFI-26 is an $α$-truxillic acid 1-naphthyl monoester that competitively inhibits the activities of FABP5 and FABP7 and produces antinociceptive and anti-inflammatory effects in mice. The synthesis of SBFI-26 yields several stereoisomers, and it is not known how the inhibitor binds the transporters. Here we report co-crystal structures of SBFI-26 in complex with human FABP5 and FABP7 at 2.2 and 1.9 Å resolution, respectively. We found that only $(S)$-SBFI-26 was present in the crystal structures. The inhibitor largely mimics the fatty acid binding pattern, but it also has several unique interactions. Notably, the FABP7 complex corroborates key aspects of the ligand binding pose at the canonical site previously predicted by virtual screening. In FABP5, SBFI-26 was unexpectedly found to bind at the substrate entry portal region in addition to binding at the canonical ligand-binding pocket. Our structural and binding energy analyses indicate that both $R$ and $S$ forms appear to bind the transporter equally well. We suggest that the $S$ enantiomer observed in the crystal structures may be a result of the crystallization process selectively incorporating the $(S)$-SBFI-26–FABP complexes into the growing lattice, or that the $S$ enantiomer may bind to the portal site more rapidly than to the canonical site, leading to an increased local concentration of the $S$ enantiomer for binding to the canonical site. Our work reveals two binding poses of SBFI-26 in its target transporters. We surmise this knowledge will guide the development of more potent FABP inhibitors based upon the SBFI-26 scaffold.

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

Intricate Magnetic Landscape in Antiferromagnetic Kagome Metal TbTi 3 Bi 4 and Interplay with Ln 2– x Ti 6+ x Bi 9 (Ln: Tb···Lu) Shurikagome Metals

Here we present the discovery and characterization of the kagome metal TbTi 3 Bi 4 in tandem with a new series of compounds, the Ln 2–x Ti 6+x Bi 9 (Ln: Tb–Lu) shurikagome metals. We previously reported on the growth of the LnTi 3 Bi 4 (Ln: La–Gd 3+ , Eu 2+ , Yb 2+ ) family, a chemically diverse and exfoliable series of kagome metals with complex and highly anisotropic magnetism. However, unlike the La–Gd analogs, TbTi 3 Bi 4 cannot be synthesized by our previous methodology due to phase competition with crystals of Ln 2–x Ti 6+x Bi 9 (x ~ 1.7–1.2). Here we discuss the phase competition between the LnTi 3 Bi 4 and Ln 2–x Ti 6+x Bi 9 families, helping to frame the difficulty in synthesizing LnTi 3 Bi 4 compounds with small Ln species and providing a strategy to circumvent the formation of Ln 2–x Ti 6+x Bi 9 . Detailed characterization of the magnetic and electronic transport properties on single crystals of TbTi 3 Bi 4 reveals a highly complex landscape of magnetic phases arising from an antiferromagnetic ground state. A series of metamagnetic transitions creates at least 5 unique magnetic phase pockets, including a 1/3 and 2/3 magnetization plateau. Further, the system exhibits an intimate connection between the magnetism and magnetotransport, exhibiting sharp switching from positive (+40%) to negative magnetoresistance (–50%). Like the LnTi 3 Bi 4 kagome metals, the Ln 2–x Ti 6+x Bi 9 family exhibits quasi-2D networks of titanium and chains of rare earth. Finally, we present the structures and some basic magnetic properties of the Ln 2–x Ti 6+x Bi 9 family alongside our characterization of the newly discovered TbTi 3 Bi 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Current and Future United States Light-Duty Vehicle Pathways: Cradle-to-Grave Lifecycle Greenhouse Gas Emissions and Economic Assessment

This article presents a cradle-to-grave (C2G) assessment of greenhouse gas (GHG) emissions and costs for current (2015) and future (2025–2030) light-duty vehicles. The analysis addressed both fuel cycle and vehicle manufacturing cycle for the following vehicle types: gasoline and diesel internal combustion engine vehicles (ICEVs), flex fuel vehicles, compressed natural gas (CNG) vehicles, hybrid electric vehicles (HEVs), hydrogen fuel cell electric vehicles (FCEVs), battery electric vehicles (BEVs), and plug-in hybrid electric vehicles (PHEVs). Gasoline ICEVs using current technology have C2G emissions of ~450 gCO2e/mi (grams of carbon dioxide equivalents per mile), while C2G emissions from HEVs, PHEVs, H2 FCEVs, and BEVs range from 300–350 gCO2e/mi. Future vehicle efficiency gains are expected to reduce emissions to ~350 gCO2/mi for ICEVs and ~250 gCO2e/mi for HEVs, PHEVs, FCEVs and BEVs. Utilizing low-carbon fuel pathways yields GHG reductions more than double those achieved by vehicle efficiency gains alone. Levelized costs of driving (LCDs) are in the range $0.25–$1.00/mi depending on timeframe and vehicle-fuel technology. In all cases, vehicle cost represents the major (60–90%) contribution to LCDs. Currently, HEV and PHEV petroleum-fueled vehicles provide the most attractive cost in terms of avoided carbon emissions, although they offer lower potential GHG reductions The ranges of LCD and cost of avoided carbon are narrower for the future technology pathways, reflecting the expected economic competitiveness of these alternative vehicles and fuels.

Cradle-to-grave↗
DOE OSTI2017

Highly Permeable AlPO-18 Membranes for N 2 /CH 4 Separation

Herein we demonstrate that AlPO-18 membranes can separate N2/CH4 gas mixtures at unprecedented N2 permeances. The best membranes separated N2/CH4 mixtures with N2 permeances as high as 3076 GPU and separation selectivities as high as 4.6. Gas mixture separation data, N2 and CH4 adsorption isotherms, ideal adsorbed solution theory (IAST), and breakthrough experiments were collected to understand the separation mechanisms. Competitive adsorption and differences in diffusivities were identified as the prevailing separation mechanisms. Differences in diffusivity played a more dominant role than the competitive adsorption, and led to nitrogen selective membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Uranium Resource Recovery from Desalination Plant Feed and Reject Water Using Amidoxime Functionalized Adsorbent

With global demand for nuclear power expected to rise, new nuclear fuel resources must be explored to ensure the viability and sustainability of nuclear power. Uranium recovery from seawater is one potential source, though the low concentration of uranium in seawater is a significant obstacle. As a concentrate of seawater, desalination brine reject would have a significantly higher uranyl concentration. In this work, the adsorption of uranium and competing ions in brine reject is investigated. Adsorption experiments were performed over 84 days in 5-gallon batch tanks with amidoxime adsorbents and samples taken from the feed seawater and reverse osmosis brine reject of the Tampa Bay Desalination Plant. The aqueous concentration and adsorbed mass of uranium, zinc, copper, iron, vanadium, calcium, and magnesium were determined through inductively coupled plasma mass spectroscopy. Aqueous adsorption modeling was used to simulate speciation and adsorption of these ions under the experimental conditions. The adsorbed mass of uranium in seawater was 6.22 mg/g adsorbent which declined to 3.95 mg/g in brine. This is a result of increased competition from iron and vanadium whose adsorbed masses increased from 1.06 to 3.00 mg/g and 1.05 to 2.67 mg/g, respectively. Good agreement between experimental and predicted results was obtained for all ions in seawater. Uranium adsorption was overpredicted in brine which may be attributed to the presence of other competing ions and the system not being at equilibrium. Furthermore, results demonstrate that the influence of competing ions, such as those of iron and vanadium, on uranium adsorption would need to be reduced for brine reject to become a significant uranium resource.

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

Coupled NO and C 3 H 6 Trapping, Release and Conversion on Pd/BEA: Evaluation of the Lean Hydrocarbon NO x Trap

Automotive emission control catalysts are not effective in eliminating CO, hydrocarbons (HCs), and NO x during engine cold start (below 200 °C). In this study, the effectiveness of coupled low-temperature NO x and C 3 H 6 trapping and conversion on the model lean HC NO x trap (LHCNT) consisting of a washcoated Pd/BEA monolith was examined. Transient uptake and release experiments were conducted to obtain insight regarding competitive adsorption, release temperature, conversion activity, and water impact. NO and C 3 H 6 uptake were found to be mutually inhibitive because of competition for adsorption on Brønsted acid sites. During desorption, the existence of multiple NO sorption sites was established. Although C 3 H 6 inhibited NO adsorption on some of these sites, it delayed NO x desorption to higher temperatures. Furthermore, above 200 °C, Pd/BEA was able to catalyze the oxidation of stored HCs and exhibited NO x reduction activity. Addition of water inhibited both NO x and C 3 H 6 uptake, but the inhibition was lessened through a high-temperature thermal pretreatment. Overall, Pd/BEA demonstrates a combination of inhibiting and promoting coupling effects during uptake and release and exhibits activity for both NO x reduction and C 3 H 6 oxidation. Lastly, the findings provide guidance for developing improved LHCNT materials.

42 ENGINEERING↗
DOE OSTI2021

Influence of the Cubic Sublattice on Magnetic Coupling between the Tetrahedral Sites of Garnet

Here, we present a study on the nuclear and magnetic structures of two iron-based garnets with magnetic cations isolated on tetrahedral sites. Ca 2 YZr 2 Fe 3 O 12 and Ca 2 LaZr 2 Fe 3 O 12 offer an interesting comparison for examining the effect of increasing cation size within the diamagnetic backbone of the garnet crystal structure, and how such changes affect the magnetic order. Despite both systems exhibiting well-pronounced magnetic transitions at low temperatures, we also find evidence for diffuse magnetic scattering due to a competition between the nearest-neighbor, next nearest-neighbor, and so on, within the tetrahedral sites. This competition results in a complex noncollinear magnetic structure on the tetrahedral sublattice creating a mixture of ferro- and antiferromagnetic interactions above the long-range ordering temperature near 20 K and suggests that the cubic site of the garnet plays a significant role in mediating the superexchange interactions between tetrahedral cations.

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

Modeling the Conformer-Dependent Electronic Absorption Spectra and Photolysis Rates of Methyl Vinyl Ketone Oxide and Methacrolein Oxide

Criegee intermediates are important atmospheric oxidants, formed via the reaction of ozone with volatile alkenes emitted into the troposphere. Small Criegee intermediates (e.g., CH 2 OO and CH 3 CHOO) are highly reactive, and their removal via unimolecular decay or bimolecular chemistry dominates their atmospheric lifetimes. As the molecular complexity of Criegee intermediates increases, their electronic absorption spectra show a bathochromic shift within the solar spectrum relevant to the troposphere. In such cases, solar photolysis may become a competitive contributor to their atmospheric removal. In this article, we report the conformer-dependent simulated electronic absorption spectra of two four-carbon-centered Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). Both MVK-oxide and MACR-oxide contain four low-energy conformers, which are convoluted in the experimentally measured spectra. Here, we deconvolute each conformer and estimate contributions from each of the four conformers to the experimentally measured spectra. We also estimate the photolysis rates and predict that solar photolysis should be a more competitive removal process for MVK-oxide and MACR-oxide (cf. CH 2 OO and CH 3 CHOO).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗