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At least 1,153 records · Page 64

Murine thymic lymphoma is associated with a species-specific hematopoietic progenitor cell subpopulation

Many strains of laboratory mouse are uniquely susceptible to the development of T cell lymphoma/leukemia, either spontaneously or as a result of chemical or radiation exposure. In contrast, T cell leukemias or lymphomas which are relatively uncommon in human populations, are not easily induced by radiation, and are not generally associated with chemotherapy or chemical exposure. Evidence is presented to suggest that differences in the susceptibility to the development of these malignancies is related to subtle but important variations in the regulation of hematopoietic stem cell differentiation between these two species.

Non-NASA Center↗

Mixing Study for the Modification of H-Canyon Tank 31 and 32 Recirculation Lines Via M-Star®

As a part of the Accelerated Basin De-Inventory (ABD) program Tanks 31 or 32 will be re-purposed to support increasing the number of annual Material Test Reactor (MTR) and High Flux Isotope Reactor (HFIR) dissolutions. The proposed plan will allow Tanks 31 or 32 to be used as the dissolver cold chemical solution makeup tank and storage tank. The dissolver cold chemicals are 50% nitric acid, process water, mercuric nitrate, and gadolinium nitrate. Tanks 31 and 32 are 9 ft. (outer diameter) x 36 ft, horizontal, and can hold approximately 56,000 liters (15,000 gallons) each. One full volume of Tanks 31 or 32 can support 4 HFIR 6.4D equivalent batches. Both tanks are equipped with liquid level instrumentation. Tank 31 is equipped with 1 pump used for transfer and recirculation while Tank 32 is equipped with two pumps, one for transfer and the other for recirculation. Each of the pumps is equipped with sample taps. The tanks do not have specific gravity instrumentation, an agitator, or a sampler. Piping modifications will also be performed to supply the tank with cold chemicals. The current dissolver chemical composition is 5.0 -8.5M HNO3 and ~0.2 g Gd/L. The recirculating pump connected to Tank 31 is rated for a flowrate 175 gpm while the pump connected to Tank 32 is rated for a flowrate 50 gpm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

MFiX: Fractional-Step Method Implementation

A comprehensive, multiphase computational fluid dynamics (CFD) simulation solves several coupled transport equations including continuity, momentum, species, and energy. Chemical reactions further couple these equations through heats of reaction and rates of formation of products and rates of destruction of reactants. A fractional-step method separates changes attributed to chemical reactions from transport phenomena like convection and diffusion. When the governing equations are split into the transport and reacting components, efficient and independent methodologies can be exploited to solve the different systems. Specifically, discretization of field variable transport equations results in large, sparse matrices which are loosely coupled. These systems are solved in succession using iterative techniques that take advantage of the matrix structure. In contrast, chemical reactions tightly couple field variables locally within the domain (e.g., within a single computational cell) resulting in low dimensional but dense, nonlinear systems that are better solved using direct integration techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗

Describing and Measuring the Chemical Signatures of Life

Here we discuss an approach to remotely detecting extraterrestrial life forms on other planets or their moons by detection of specific types of organic molecules. The life entities to be detected would be presently active life forms, or those that are only recently dormant. The only place beside Earth's moon where humans have actually examined surface soils for the presence of organic molecules is Mars. This was accomplished using mass-spectrometry during the Viking mission, and results were negative. The lack of organic moieties, if they ever were present, probably resulted form their destruction over geologic time frames by the extraordinarily reactive surface soils found there. Thus, on Mars, detection of organic signatures of life probably would be possible only in subsurface soils, or perhaps in polar regions.

Crawford, R. L.↗

Lunar Dust Mitigation: A Guide and Reference: First Edition (2021)

On the surface of the Moon, lunar dust specifically presents unique challenges to operations long-term due to regolith particles’ ubiquitous presence in the lunar environment, potential to electrostatically charge and possible chemical reactivity. Whether to avoid exposure, try to remove or simply to tolerate lunar dust infiltrating a system becomes a complex question involving length of required service life, dust effects and critical risks, mass and complexity trades for the entire system. This publication provides a snapshot of advice from topical experts for specific areas of concern to systems targeted for deployment on the lunar surface. Following introductory overview commentary, dust mitigation approaches appropriate to the lunar surface are first addressed for typically static structures such as optical surfaces, radiators, and other thermal control surfaces, followed by regolith exposure concerns for communications equipment and non-optical sensors. The broad topic of mechanisms and mechanical assemblies is broken down to address relevant component level concerns, such as for bearings and for seals. “Soft goods” components of space suits (fabric) specific concerns are discussed, followed finally by brief coverage of human health issues and concerns, though the emphasis of this publication remains with components directly exposed to the harsh lunar surface environment. A description of some lunar surface hazard details, in particular characteristics of lunar surface dust, follows in Appendix A, and more detailed explanations of quantification issues for particulates are in Appendix B. The simple inertial removal of particles from a surface is discussed in Appendix C, followed by a summary of terrestrial best practices for dust mitigation recommended within select industries in Appendix D. The aggregated bibliography of references, while extensive and very useful, should not be construed to be exhaustive and can serve as a constructive start.

dust↗

Molecular-Scale Insights into the Heterogeneous Interactions between an m -Terphenyl Isocyanide Ligand and Noble Metal Nanoparticles

The structural and chemical properties of metal nanoparticles are often dictated by their interactions with molecular ligand shells. These interactions are highly material-specific and can vary significantly even among elements within the same group or materials with similar crystal structure. In this study, we surveyed the heterogeneous interactions between an m-terphenyl isocyanide ligand and Au and Ag nanoparticles (NPs) at the single-molecule limit. Specifically, we found that the ligation behavior with this molecule differs significantly between that of Au and AgNPs. Surface-enhanced Raman spectroscopy measurements revealed unique enhancement factors for two molecular vibrational modes between two metal surfaces, indicating different ligand binding geometries. Molecular-level characterization using scanning tunneling microscopy allowed us to directly visualize these variations between Ag and Au surfaces, which we assign as two distinct binding mechanisms. This molecular-scale visualization provides clear insights into the different ligand–metal interactions as well as the chemical behavior and spectroscopic characteristics of isocyanide-functionalized NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helium Ion Microscopy with Secondary Ion Mass Spectrometry for Nanoscale Chemical Imaging and Analysis of Polyolefins

To date, chemical imaging of polymers and polymer blends has been primarily accomplished using time-of-flight secondary ion mass spectrometry (ToF-SIMS) to directly visualize the distribution of components in a complex material with spatial resolution ranging from 100 nm to 5 μm. However, in many cases, this resolution falls far short of visualizing interfaces directly. To overcome these limitations, recent work has focused on developing a SIMS detection system based on a helium ion microscope (HIM) enabling chemical imaging with a demonstrated ~14 nm spatial resolution. Here, we utilize HIM-SIMS for differentiation between the olefin-based polymers of polyethylene (PE) and polypropylene (PP). We illustrate both analyses for separating PE and PP using specific mass fragment ratios as well as demonstrate spatially resolved imaging of phase-separated domains within PE. Altogether, we demonstrate the abilities of HIM-SIMS as a multimodal chemical technique for imaging and quantification of polyolefin interfaces, which could be more broadly applied to the analysis of more complex polymeric systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Review of low salinity waterflooding in carbonate rocks: mechanisms, investigation techniques, and future directions

This review analyses the fundamental thermodynamic theory of the crude oil-brine-rock (COBR) interface and the underlying rock-brine and oil-brine interactions. Next, the available data are reviewed to outline potential mechanisms responsible for increased oil recovery from low salinity waterflooding (LSWF). We propose an approach to studying LSWF and identify the key missing links that are needed to explain observations at multiple length scales. The synergistic effect of LSWFon other chemical enhanced oil recovery methods such as surfactant, alkaline, nanoparticle and polymer flooding are also outlined. We specifically highlight key uncertainties that must be overcome to fully implement the technique in the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The impacts of charge transfer, localization, and metallicity on hydrogen retention and transport capacity

Solid state hydrides such as early transition metal hydrides are of inestimable importance for the future of hydrogen energy and are actively being investigated for energy conversion and storage applications such as fuel cells, solid-state batteries and neutron moderators. The retention and transport behavior of hydrogen in these hydrides has a huge role on the extended performance of components. While early transition-metal-based compounds exhibit many peculiar properties due to their unique correlated electronic signatures arising from -orbital electrons, the fundamental chemistry and transport behavior of hydrogen in such hydrides is not well understood. In the present work, using density functional theory, a highly intricate bonding feature is revealed through the theoretical investigation of the electronic structure of early transition metal hydrides YH 2 and ZrH 2 . In particular, a pronounced charge transfer from the transition element to H, results in localized electron densities at deep energy levels. The interplay between intrinsic charge transfer, charge localization, and metallicity in YH 2 and ZrH 2 leads to strong chemical bonding between metal and hydrogen atoms and large energy barriers for the migration of hydrogen vacancies. Specifically, hydrogen vacancies are found to be stable in the neutral state due to electron screening effects, accompanied by substantially high migration barriers between 0.8–1.2 eV along different crystallographic directions. In contrast, recent literature shows the migration barrier for charged H vacancies in insulating s-block metal hydrides lie between 0.1–0.4 eV, which is suitable for fast conduction applications. This pivotal electron structure difference exploited between early transition metal hydrides and alkali/alkaline earth metal hydrides determines extended hydrogen retention in these early transition metal hydrides. Finally, this work explains fundamental differences between the electronic structure of s-block and d-block metal hydrides, and its impact on the mobility of hydrogen vacancies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Post-irradiation examination of UN-Mo-W fuels for space nuclear propulsion

The National Aeronautics and Space Administration's return to space nuclear propulsion stems from the need for a more efficient method of space travel. Nuclear thermal propulsion systems have been shown to be two times more efficient than chemical propulsion. NASA's Sirius program was created to fabricate and test fuels for space nuclear propulsion, specifically to determine their performance under prototypical startup conditions. The Sirius project featured 4 test capsules, Sirius-1 featured uranium nitride fuel dispersed in a matrix of tungsten and rhenium, while Sirius-2A, -2B, and -3 featured uranium nitride-molybdenum-tungsten fuel (UN-Mo-W). This study discusses the Sirius-2A and -2B irradiation experiments at the Idaho National Laboratory, specifically their performance under irradiation at the Transient Reactor Test Facility. It was found that the fuel samples overall did not exhibit significant cracking, though the Sirius-2A fuel did have one large crack on the surface of the fuel. There was minimal hydrogen absorption in the samples, though it is unknown if the absorption occurred during irradiation or during fabrication. Mechanical testing indicated that the UN fuel demonstrated ceramic behavior as expected, and the Mo/W matrix demonstrated linear elastic behavior to failure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ab Initio Dynamics of Graphene and Graphyne Electrodes in Vacuum and in the Presence of Electrolytes

Graphene and graphyne electrodes are both relevant for electrochemical energy storage applications due to their unique physical, chemical, and electronic properties. Graphyne has been considered even more attractive than graphene due to its larger specific surface area, greater electronic mobility, and intrinsic band gap. The analyses presented in this work reveal relevant features of graphyne in an interaction with an electrolyte that can be useful for practical applications. Although there is already a considerable volume of work on graphyne, the analysis of its properties taking into account the dynamics of its network and the interaction with the condensed medium has not yet been presented. Here, ab initio molecular dynamics simulations were performed to study the energetic, structural, spectroscopic, and electronic properties of graphene and graphyne electrodes in vacuum and in the presence of an electrolyte (EMIM-BF 4 ). A detailed analysis of the electrode–electrolyte interaction is reported for both systems. Structural features are presented in terms of both radial and spatial distribution functions and angular orientation distributions. Power spectral analyses and molecular orbital maps provided important insights into the intermolecular interactions in graphene and graphyne systems, describing the main differences as well as revealing similarities between them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Submicrometer spectromicroscopy of UO 2 aged under high humidity conditions

We report the oxidation of uranium dioxide is a complicated process, depending on factors including humidity, temperature, and microstructure. To further determine the characteristics of this process, UO 2 particles were allowed to age and agglomerate under 98% relative humidity at room temperature for 378 days. A focused ion beam (FIB) section of this agglomeration was then measured at the O K-edge, U N 5 -edge, and C K-edge using the scanning transmission x-ray microscope (STXM) at the Advanced Light Source. O K-edge and U N 5 -edge x-ray absorption measurements allowed for the elemental and chemical species mapping of the agglomerates and indicated the formation of schoepite at the submicrometer scale in specific locations. Non-negative matrix factorization was employed to elucidate the main components at the O K-edge, which were uranyl (schoepite) formed primarily at the interface of the sample with controlled atmosphere, a UO 2 -like bulk component present in the majority of the sample, and an oxygen species present at the surface of the FIB section, which is likely adsorbed water. STXM spectromicroscopy measurements at the U N 5 -edge measurements also confirmed the location of oxidized uranium. This analysis is a valuable insight into the formation of schoepite on UO 2 and shows the sensitivity to and utility of STXM spectromicroscopy for uranium speciation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accelerator-Based Production of Scandium Radioisotopes for Applications in Prostate Cancer: Toward Building a Pipeline for Rapid Development of Novel Theranostics

In the field of nuclear medicine, the β + -emitting 43 Sc and β - -emitting 47 Sc are promising candidates in cancer diagnosis and targeted radionuclide therapy (TRT) due to their favorable decay schema and shared pharmacokinetics as a true theranostic pair. Additionally, scandium is a group-3 transition metal (like 177 Lu) and exhibits affinity for DOTA-based chelators, which have been studied in depth, making the barrier to implementation lower for 43/47 Sc than for other proposed true theranostics. Before 43/47 Sc can see widespread pre-clinical evaluation, however, an accessible production methodology must be established and each isotope’s radiolabeling and animal imaging capabilities studied with a widely utilized tracer. As such, a simple means of converting an 18 MeV biomedical cyclotron to support solid targets and produce 43 Sc via the 42 Ca(d,n) 43 Sc reaction has been devised, exhibiting reasonable yields. The Nat Ti(γ,p) 47 Sc reaction is also investigated along with the successful implementation of chemical separation and purification methods for 43/47 Sc. The conjugation of 43/47 Sc with PSMA-617 at specific activities of up to 8.94 MBq/nmol and the subsequent imaging of LNCaP-ENZaR tumor xenografts in mouse models with both 43/47 Sc-PSMA-617 are also presented.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

The effect of alloy composition on the mechanism of stress-corrosion cracking of titanium alloys in aqueous environments

A detailed study was made of the relation between the size distribution of Ti3Al particles in a Ti-8Al alloy and the tensile properties measured in air and in saltwater. The size distribution of Ti3Al was varied by isothermal aging for various times at temperatures in the range 770 to 970 K (930 to 1290 F). The aging kinetics were found to be relatively slow. Quantitative measurements of the particle coarsening rate at 920 K (1200 F) showed good agreement with the predicted behavior for coarsening controlled by matrix diffusion, and suggested that the specific free energy of the Ti3Al alpha interface in negligible small. In all cases, the Ti3Al particles were sheared by the glide dislocations. It was concluded that there is a definite correlation between the presence of deformable Ti3Al particles and an alloy's susceptibility to aqueous stress corrosion cracking. Furthermore, the appearance of the surface slip lines and the dislocation substructure in deformed specimens suggest that the specific effect of the Ti3Al particles is to cause a nonhomogeneous planar slip character and an enhanced chemical potential of the slip bands.

Wood, R. A.↗

Improved methods for counting bacteria in physiological fluids

Bacterial population detection is based on detection of adenosine triphosphate (ATP), chemical present in all living matter. Amount of ATP in sample, after chemically removing all nonbacterial ATP, is directly related to bacterial population. Sensitivity is improved by concentration step; specificity is improved by lowering pH of solution.

Picciolo, G. L.↗

Detonation propulsion for high pressure environments

One limitation encountered by chemical rocket propulsion in high pressure planetary atmospheres is illustrated by the conflict between the dependence of specific impulse on the ratio of chamber pressure to ambient pressure and the dependence of the motor structural design on the difference between the pressures. This work proposes to resolve the difficulty by employing detonating propellant in which the high pressures necessary for efficient propulsion are developed over a short time and need not be contained statically. Experimental results are presented to substantiate this claim of relatively high performance, together with an analytical development that approximately describes the flow dynamics.

Varsi, G.↗

Computer Program for the Calculation of Multicomponent Convective Diffusion Deposition Rates from Chemically Frozen Boundary Layer Theory

The computer program based on multicomponent chemically frozen boundary layer (CFBL) theory for calculating vapor and/or small particle deposition rates is documented. A specific application to perimter-averaged Na2SO4 deposition rate calculations on a cylindrical collector is demonstrated. The manual includes a typical program input and output for users.

Gokoglu, S. A.↗