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At least 577 records · Page 32

Electron Binding Energy Spectra of Al n Mo – Clusters: Measurements, Calculations, and Theoretical Analysis

Results of photoelectron spectroscopy measurements and density functional theory complemented with correction scheme calculations on electron binding energy (EBE) spectra of anionic Al n Mo, n = 3–5 and 7, clusters are presented and analyzed. The analysis points to the important role of dynamical fluxionality and multiplicity of structural forms as contributing factors in the measured spectra. Finally, using the example of Al 4 Mo – as a paradigmatic case, the separate roles of size, structure/symmetry, and composition in evolving the EBE spectra of precursor pure clusters (in this case, Al 4 – and Al 5 – ) into those of bimetallic clusters are demonstrated utilizing a new methodology we developed recently.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comment on the Predicted Size of Cycle 23 Based on the Inferred Three-Cycle Quasi-Periodicity of the Planetary Index Ap

Recently, Ahluwalia [1998] reviewed the solar and geomagnetic data for the last 6 decades and remarked that these data "indicate the existence of a three-solar-activity-cycle quasi-periodicity in them." Futhermore, on the basis of this inferred quasi-periodicity, he asserted that cycle 23 represents the initial cycle in a new 3-cycle string, implying that it "will be more modest (a la cycle 17) with an annual mean sunspot number count of 119.3 +/- 30 at the maximum," a prediction that is considerably below the consensus prediction of 160 +/- 30 by Joselyn et al. [1997] and of similar predictions by others based on a variety of predictive techniques. Several major sticking points of Ahluwalia's presentation, however, must be redressed, and these issues form the basis of this comment. In particular, it is shown that Ahluwalia used inappropriate values of the Ap index in his analysis, that the inferred 3-cycle relationship which Ahluwalia claims for both Ap and SSN does not exist for the previous 6-cycle interval (prior to cycle 17) for SSN, that his inferred fit is only of marginal statistical significance (having r = 0.81), and that two alternative precursor fits (both with r = 0.96 or greater) exist which strongly suggest that R max for cycle 23 will be much larger than forecast by Ahluwalia (namely, about 168-187). Thus, caution must be exercised in accepting Ahluwalia's findings.

Hathaway, David H.↗

Towards Prognostics of Power MOSFETs: Accelerated Aging and Precursors of Failure

This paper presents research results dealing with power MOSFETs (metal oxide semiconductor field effect transistor) within the prognostics and health management of electronics. Experimental results are presented for the identification of the on-resistance as a precursor to failure of devices with die-attach degradation as a failure mechanism. Devices are aged under power cycling in order to trigger die-attach damage. In situ measurements of key electrical and thermal parameters are collected throughout the aging process and further used for analysis and computation of the on-resistance parameter. Experimental results show that the devices experience die-attach damage and that the on-resistance captures the degradation process in such a way that it could be used for the development of prognostics algorithms (data-driven or physics-based).

Celaya, Jose R.↗

Using Skyline to Analyze Data-Containing Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry Dimensions

Recent advances in ion mobility spectrometry (IMS) have illustrated its power in determining the structural characteristics of a molecule, especially when coupled with other separations dimensions such as liquid chromatography (LC) and mass spectrometry (MS). However, these three separation techniques together greatly complicate data analyses, making better informatics tools essential for assessing the resulting data. In this manuscript, Skyline was adapted to analyze LC-IMS-CID-MS data from numerous instrument vendor datasets and determine the effect of adding the IMS dimension into the normal LC-MS molecular pipeline. For the initial evaluation, a tryptic digest of bovine serum albumin (BSA) was spiked into a yeast protein digest at seven different concentrations, and Skyline was able to rapidly analyze the MS and CID-MS data for 38 of the BSA peptides. Calibration curves for the precursor and fragment ions were assessed with and without the IMS dimension. In all cases, addition of the IMS dimension removed noise from co-eluting peptides with close m/z values, resulting in calibration curves with greater linearity and lower detection limits. This study presents an important informatics development since to date LC-IMS-CID-MS data from the different instrument vendors is often assessed manually and cannot be analyzed quickly. Because these evaluations require days for the analysis of only a few target molecules in a limited number of samples, it is unfeasible to evaluate hundreds of targets in numerous samples. Thus, this study showcases Skyline’s ability to work with the multidimensional LC-IMS-CID-MS data and provide biological and environmental insights rapidly. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Structural synthesis: Precursor and catalyst

More than twenty five years have elapsed since it was recognized that a rather general class of structural design optimization tasks could be properly posed as an inequality constrained minimization problem. It is suggested that, independent of primary discipline area, it will be useful to think about: (1) posing design problems in terms of an objective function and inequality constraints; (2) generating design oriented approximate analysis methods (giving special attention to behavior sensitivity analysis); (3) distinguishing between decisions that lead to an analysis model and those that lead to a design model; (4) finding ways to generate a sequence of approximate design optimization problems that capture the essential characteristics of the primary problem, while still having an explicit algebraic form that is matched to one or more of the established optimization algorithms; (5) examining the potential of optimum design sensitivity analysis to facilitate quantitative trade-off studies as well as participation in multilevel design activities. It should be kept in mind that multilevel methods are inherently well suited to a parallel mode of operation in computer terms or to a division of labor between task groups in organizational terms. Based on structural experience with multilevel methods general guidelines are suggested.

Schmit, L. A.↗

Design of Zn Chalcogenide Shells for Emissive Ga-Rich In 1– X Ga X As Quantum Dots Synthesized in Molten Salts

Colloidal quantum dots (QDs) have seen expanded applications in optoelectronics from visible to near-infrared (NIR) wavelengths. However, the options for QDs with bright and size-tunable emission in the NIR region are mostly limited to heavy-metal-based (Pb, Cd, Hg) semiconductors. Here, Ga-rich In 1–X Ga X As QDs with zinc chalcogenide shells are demonstrated as candidates for NIR emitters. Based on new developments in inorganic molten salt chemistry, we synthesized colloidal In 1–X Ga X As QDs containing up to 85% gallium with high crystallinity based on Raman and XRD analyses. Zinc selenide and sulfide shells with different morphologies were grown on In 1–X Ga X As QDs by controlling the Zn precursor chemistry. Despite the nominally reduced lattice mismatch in the In 1–X Ga X As/ZnSe heterostructure, a ZnS shell was found to be a much more effective passivation material: In 1–X Ga X As/ZnS core–shell QDs show a photoluminescence quantum yield (PL QY) of about 30% versus 11% for ZnSe shells. In conclusion, based on the analysis of PL decay and transient absorption (TA) dynamics, we surmise that electron trapping is the major reason for efficiency loss, providing a clear heterostructure design principle for realizing efficient NIR-emitting In 1–X Ga X As QDs.

Electron trapping↗

Defining Lipidomic Responses to Coronavirus Infection

Highly pathogenic human coronavirus infection can cause a severe atypical, rapid onset pneumonia with a mortality rate of up to 10% for severe acute respiratory syndrome coronavirus 1 (SARS-CoV 1), 35% for Middle East respiratory syndrome coronavirus (MERS-CoV), or 1% for severe acute respiratory syndrome coronavirus 2 (SARS-CoV 2 causative agent of COVID 19). While medical countermeasures successfully controlled the worldwide SARS-CoV epidemic, the MERS-CoV epidemic is still ongoing and continues to be a concern for travelers in the Middle East and the multi-year SARS-CoV 2 pandemic underscore the importance of defining biomarkers that are diagnostic and/or predictive of severe disease outcomes for respiratory viruses. Systems biology approaches provide global snapshots of infection induced changes in host cells/tissues and provide extremely rich datasets for understanding host pathogen interactions. Metabolites, especially lipids, are critical for viral replication but less is understood about infection induced changes to lipids due to limits in lipid species detection and identification. To characterize how individual lipid species and proteins with lipid associated functions contribute to highly pathogenic human coronavirus replication and disease severity, existing datasets were probed to determine cell type specific lipid responses to MERS-CoV infection and verification studies were performed to determine if modification of the host lipid signature (by inhibiting enzymatic functions that produce specific lipid species) can perturb CoV replication in human lung cells. MERS-CoV infects human lung epithelial, endothelial and fibroblast cells. All three cell types were infected with MERS-CoV and samples collected to analyze lipids, proteins, metabolites, and transcripts from 12 to 48 hours post infection. Time matched mock-infected cells were collected in parallel for each cell type. Following sample and statistical analysis, functional enrichment and bioinformatic analysis was performed to identify differentially expressed lipids and proteins. Two lipid species were found to be significantly upregulated following MERS-CoV infection, ceramides, and triacylglycerol both of which are indicative of cells undergoing apoptotic cell death. In contrast, sphingomyelins (lipid molecules that can serve as a precursor for one pathway for ceramide synthesis) had significantly decreased expression in MERS-CoV infected cells. An inhibitor of acid sphingomyelinase (that converts sphingomyelin to ceramides and phosphorylcholine) reduced MERS-CoV replication suggesting that production of ceramides is key for successful viral replication and transmission. Acyl-CoA-synthetase 3 (ACSL3), the only protein whose function is lipid associated and had increased differential expression in our dataset, regulates the synthesis of triacylglycerol (increased expression). Inhibitors that directly block ACSL3 (Triacsin C) but not steps later in the triacylglycerol synthesis pathway (Etomoxir) inhibit MERS-CoV replication suggesting that triacylglycerol production and/or ACSL3 activity is also key for viral replication. ACSL3 expression is also upregulated in lung cancer cells and is predicted to promote continued cell viability which would also enhance viral replication. The differentially expressed lipid and lipid-associated protein species identified in our studies suggest that MERS-CoV infection is activating cellular death pathways to limit the number of cells that become infected but also stimulating the production of lipid-associated enzymes that can prolong host cell viability and the amount of time progeny virions can be produced and released. As the inhibitors that worked against MERS-CoV infection were also efficacious against SARS-CoV 2 infection, countermeasures that target these host pathways may provide novel ways to block highly pathogenic human coronavirus infection and/or prevent severe disease outcomes.

59 BASIC BIOLOGICAL SCIENCES↗

Hydrodynamic characterization of the redox chemistry of crown-encapsulated uranyl complexes

The redox properties of actinide-containing species strongly influence their reactivity, speciation, and interfacial behavior, but the experimental quantification of the electrochemical characteristics of molecular actinide complexes in nonaqueous media has not received the attention it deserves. Here, results from hydrodynamic methods and electrochemical simulations of U(VI)/U(V) redox are reported, including quantification of heterogeneous electron-transfer kinetics and estimation of chemical reversibility of U(VI)/U(V) interconversion at electrodes in acetonitrile-based electrolyte. The complexes investigated are recently reported U(VI) and U(V) complexes in which the uranyl ion (UO 2 n+ ) is encapsulated in a macrocyclic 18-crown-6-like moiety templated by a Pt(II) center. These complexes feature the most positive value U VI /U V reduction potential yet reported and are thus particularly relevant to study of facile U(V) generation from U(VI) precursors as well as uranium electroanalysis. Rotating disk electrode (RDE) studies have been used to quantify the diffusion coefficients of the U(VI) and U(V) complexes, and standard heterogeneous electron transfer rate constants ( k 0 ) for the redox have been determined using a conventional Koutecký-Levich analysis. Rotating ring-disk electrode (RRDE) studies have been used to directly interrogate the chemical reversibility of U(VI)-U(V) interconversion, confirming that reduction of the U(VI) complex at an Au disk is associated with formation of the U(V) analogue that can be readily re-oxidized at a Pt ring under hydrodynamic (rotating) conditions. Because measurements of the type reported here are generally associated with current flows that are larger than those found in corresponding quiescent (unstirred) conditions, our findings suggest that hydrodynamic methods could be advantageous for design of electroanalytical approaches to detection of actinide species and study of their redox properties.

actinides↗

Exchange of sulfur between the free troposphere, marine boundary layer, and the sea surface

A steady state analysis has been made of the sources and sinks of sulfur in the remote marine atmosphere and of the steady state exhanges of SO2 and sulfate between the sea, boundary layer, and free troposphere. Two situations were examined: an area of high biological productivity (Gulf of Guinea) and an area of low productivity (tropical Atlantic). The results of the analysis suggest that about one-third of the background concentrations of SO2 and excess sulfate observed in the remote marine atmosphere mixes in from the free troposphere, with the balance, about 100 micrograms S/sq m per day, attributed to the local oxidation of reduced sulfur-bearing precursors in the boundary layer.

Kritz, M. A.↗

Comparison and analysis of aircraft measurements and mesoscale atmospheric chemistry model simulations of tropospheric ozone

The Regional Acid Deposition Model (RADM) has been applied to several of the field experiments which were part of the Acid Models Operational and Diagnostic Evaluation Study (Acid MODES). The experiment which was of particular interest with regards to ozone photochemistry involved horizontal zig-zag flight patterns (ZIPPER) over an area from the eastern Ohio River valley to the Adirondacks of New York. Model simulations by both the standard resolution RADM (delta x = 80 km) and the nested grid RADM (delta x = 26.7 km) compare well to measurements in the low emission regions in central Pennsylvania and upstate New York, but underestimate in the high emission upper Ohio River valley. The nested simulation does considerably better, however, than the coarse grid simulation in terms of horizontal pattern and concentration magnitudes. Analysis of NO(x) and HO(x) concentrations and photochemical products rates of ozone show that the model's response to large point source emissions is very unsystematic both spatially and temporally. This is due to the models instability to realistically simulate the small scale (subgrid) gradients in precursor concentrations in and around large point source plumes.

Pleim, Jonathan E.↗

Development of In Situ Instruments for Planetary Exploration - Unique Challenges in Design, Development, and Execution

A viewgraph presentation describing in situ instruments for NASA missions is shown. The topics include: 1) In Situ Instrumentation; 2) Planetary Extremes; 3) Mars Surface Environment; 4) Lunar Precursor Mission Environment; 5) Europa Surface Analogue; 6) Other Parameters; 7) Space In Situ Instrumentation still in its Infancy; 8) Needed Capabilities For In Situ Science; 9) Framework For Putting The Pieces Together; 10) The Wild World of Astrobiology; 11) Timeline; 12) Example: MOD; 13) In Situ Sample Analysis Laboratories are more complex; 14) technologies In Situ Sample Analysis Requires Integration of Many Emerging Advanced Concepts; 15) Supporting technologies for In Situ Laboratories; 16) Micro-laboratory example; 17) In Situ Instrument Classes; and 18) Key for Analytical Instrument:Sample Preparation.

In Situ Instrumentation↗

Flight Testing of In-Time Safety Assurance Technologies for UAS Operations

Ongoing research at NASA is driven by a strategic plan defined by the Aeronautics Research Mission Directorate and a vision for future In-Time Aviation Safety Management Systems (IASMS) as described by the National Academies. In both visions, system safety awareness and provision are expanded through increased access to relevant data; integrated analysis and predictive capabilities; improved real-time detection and alerting of domain-specific hazards; decision support, and in some cases, automated risk mitigation strategies. One primary research focus is to develop means by which more timely (i.e., “in-time”) actions may be taken to mitigate precursors, anomalies, or trends that are observed during operations. In this paper, we describe such means as a collection of Services, Functions, and Capabilities (SFCs) that are supported by an underlying information system. For example, an integrated risk assessment capability is envisioned that continuously monitors safety-related metrics and margins and recommends timely operational changes. Assessment functions and/or services can be based on data analytics and predictive models derived from heterogeneous data sets that span relevant indicator metrics and their time histories. Likewise, on-board functions can identify and reduce susceptibility to precursor conditions that have led (and can lead) to aircraft loss-of-control or out-of-control accidents. This paper summarizes development and testing of such an information system tailored to hazards anticipated for future highly autonomous flight missions near and over densely populated areas. Testing is accomplished via simulation and by using small, unmanned aircraft operating over a test range at NASA’s Langley Research Center. Flight plans and test scenarios are defined to emulate several use-cases, including package delivery; reconnaissance; fire management; and urban air taxi vertiport operations. Two test phases are summarized with Phase 1 occurring in (2019-2020) and Phase 2 ongoing (2021-present). Results focus on SFC performance, technology readiness level assessment, and requirements discovery/validation. Companion papers are cited throughout for additional details on the recent testing.

safety management↗

Phosphate-passivated mordenite for tandem-catalytic conversion of syngas to ethanol or acetic acid

Selective and stable production of C 2 oxygenates from syngas is enabled by a phosphate-passivated mordenite catalyst used in tandem with a commercial Cu/ZnO/AlMgO x catalyst. Unmodified mordenite used in this arrangement is accompanied by substantial hydrocarbon formation and carbon deposition. Therefore, phosphate groups are used to remove or significantly reduce Brønsted acidity in mordenite by capping aluminum sites. Such groups are stable to calcination and catalyst regeneration. Here, trimethylphosphite is used as a phosphate precursor because it is able to enter the 12 membered-ring pores of mordenite where hydrocarbon formation occurs, but not enter the 8 membered-ring sidepockets, where methanol carbonylation occurs selectively. The catalyst was characterized using X-ray fluorescence, X-ray diffraction, and thermal gravimetric analysis. Optionally, a third bed of Cu/ZnO/AlMgO x catalyst is able to hydrodeoxygenate acetic acid to ethanol. The C 2 oxygenate selectivity is over 96% and among the best reported in a single reactor with a syngas feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The S solubility of Cr and Al containing simulated low-activity waste glass

Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.

36 MATERIALS SCIENCE↗

Improved Solid-State Reaction Method for Scaled-Up Synthesis of Ceramic Proton-Conducting Electrolyte Materials

Protonic ceramic electrochemical cells (PCECs) represent promising technologies in the production of clean electricity, decarbonized hydrogen, chemicals, and fuels at intermediate temperatures. One of the challenges in commercializing PCECs is to produce the electrolyte materials on a large scale. The conventional solid-state reaction (SSR) method suffers from tedious synthesis procedures and low phase purity of the products due to the formation of unwanted secondary phases. Herein, we report an improved SSR (i-SSR) method for kilogram-scale production of high phase-purity electrolyte material BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3–δ (BZCYYb4411). In this method, the ball-milled precursor powders are pelletized prior to calcination, which effectively reduces the length of the diffusion paths between the components during perovskite phase formation. In this study, the synthesis procedure and calcination temperature are carefully optimized for efficient and repeatable production based on the powder crystallization behavior. A combined technoeconomic analysis and life cycle assessment modeling suggest that the i-SSR method could reduce the total production cost and greenhouse gas emissions by up to 19% and 39%, respectively, compared to the conventional SSR method. The high quality of the synthesized electrolyte material is corroborated by the excellent electrical conductivity and electrochemical performance of the fabricated PCEC cells.

36 MATERIALS SCIENCE↗

Production of bio-based lactones as monomers for a circular polymer economy

To create a circular plastics economy, new polymers are being developed that can be chemically recycled. Circular polyesters are of particular interest and to this end, lactones are ideal monomers. Here, this Review examines catalytic routes to convert diols, hydroxy acids, and dicarboxylic acids to lactones, focusing on the development of scalable, atom-economic, and energy-efficient conversions of bio-derived feedstocks. Free energy analysis is used to inform process choices, such as reactor type, reaction phase, and use of solvent. Catalyst design principles are summarized for both direct (bio-substrate to lactone) and indirect (bio-substrate to intermediate to lactone) routes. Finally, we summarize literature that shows that many lactone precursors are readily accessible from various metabolic and chemo-catalytic pathways. Transitioning to bio-based monomers offers an opportunity to reduce reliance on fossil carbon resources, but requires advanced catalytic processes informed by mechanistic insights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Can Mineral Growth by Oriented Attachment Lead to Incorporation of Uranium(VI) into the Structure of Goethite?

Oriented aggregation (OA), whereby crystals grow by successive attachment of precursor nanoparticles that are crystallographically co-aligned with the growing crystal, is a fundamental process by which many low solubility phases and minerals reach maturity in aqueous solution. Here, we investigated whether U(VI) can be incorporated into the structure of goethite that grows by OA. Wet chemical analysis and acid treatments showed that the additions of U(VI) early in the OA process hindered crystallization and increased the recalcitrant fraction of sorbed U(VI) relative to later addition of U(VI). Over time, however, the recalcitrant fraction of U(VI) decreased and converged to similar values for both early and late additions of U(VI). Electron microscopy indicated a portion of the acid resistant sorbed U(VI) was likely associated with grain boundaries between aggregating particles, not nanopores; and that these features were annealed out with increasing reaction time. Further, time elapsed imaging of U atom diffusion, that was stimulated by the electron beam, indicated that most sorbed U(VI) was not incorporated into the structure of goethite. This was confirmed and more rigorously quantified by ab initio molecular dynamics informed extended X-ray absorption fine structure spectra which indicated that only up to 5% of the recalcitrant U(VI) might be incorporated with an upper solubility limit of only U/Fe ~ 0.02 atom % in goethite where U(VI) was added early in the process. We conclude that most of the recalcitrant U(VI) is simply strongly adsorbed to the surface and that it is the uranyl oxygens that both inhibit crystallization of goethite as well as incorporation of U into the structure of goethite.

Soltis, Jennifer A.↗