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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 559 records · Page 31

X-ray diffraction studies of model compounds of thermoplastic polyimides

Several model compounds which represent aspects of the chemical structure of the Langley Research Center thermoplastic (LARC-TPI) have been synthesized for comparison studies using wide angle X-ray scattering (WAXS) as the discriminatory tool. The model compounds included N-phenylphthalimide, 3,3',4,4'-benzophenonetetracarboxylic diphthalimide, and N,N'-diphenyl-3,3',4,4'-benzophenonetetracarboxylic diphthalimide. X-ray diffraction studies of appropriate model compounds can yield information to aid in the understanding of polymeric crystallographic structure. Crystallinity and physical property changes can thus be induced into materials having complicated structures by chemical and thermal processes.

Wakelyn, N. T.↗

Per- and Polyfluoroalkyl Substances: A Preliminary Evaluation of Groundwater Contamination in the Western States

Per- and Polyfluoroalkyl Substances (PFAS) are a manufactured group of chemicals that have been used since the 1940s. PFAS break down very slowly and studies show that exposure to these chemicals may cause negative reproductive effects, developmental delays in children, increased risk of some cancers, and interference with the body’s natural hormones. On June 15, 2022, EPA issued interim updated drinking water health advisories for the two most widely studied PFAS, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). The concentrations for the health advisory limits are 0.004 parts per trillion (ppt) and 0.02 ppt respectively. Because data is often reported in combined PFOA and PFOS concentrations, and for ease of data visualization, concentrations of the two chemicals will be discussed as a single, summed value and will be compared to the combined health advisory limits of 0.024 ppt. Due to the recently published near-zero health advisory limits and the known negative health effects, a map of estimated PFAS groundwater contamination was created using ArcGIS Pro and geostatistical tools to inform the public and determine which regions are most at-risk.

54 ENVIRONMENTAL SCIENCES↗

Development Of Thermodynamic and Kinetic Simulation Tools and Testing Procedures for Enhanced Durability of Concrete Containing Industrial By-Products

This project developed screening tools that enable evaluation of alternative cementitious binders that create concretes to significantly reduce energy and emissions while remaining cost competitive on both initial and long-term costs. The team began with the viewpoint that acceptance of new cementitious binder products has a substantially greater chance of successful implementation when capital investment is not excessive and the end product has customers that have experience and resources to use this. As such, a binder system that is based on portland cement with blended using industrial by-products (alternative cementitious materials) has the potential for dramatic and meaningful impact. The team has focused on developing implementable solutions in specifications and current practice. This however requires three main factors: 1) ability to screen byproducts and alternative materials for success, 2) ability to ‘treat’ materials chemically to enhance kinetics, and 3) ability to provide predictions of performance of both binders and concrete from first principles. The project developed/refined a state of the art and scientifically based screening test for SCM called the pozzolanic reactivity test. The team developed kinetic models to simulate these materials as well as experimental approaches to alter selected reactions. Simulation tools were developed that enable the performance of concrete to be predicted based on the chemistry and reactivity of the cement and alternative SCM. Specifically, this project: • enhanced the kinetic reactivity models for use in multi-scale computational programs that use thermodynamics to predict reaction products. 2 • developed scaling models to extend thermodynamic modeling to link these models with pore structure. This enables strength, transport property, and coupled transport prediction. • developed tools to predict performance of cementitious materials using the pozzolanic reactivity test and chemical composition. The predicted properties are consistent with AASHTO R101 and the CEB-FIP model code and can be measured using associated test procedures. • demonstrated mechanical and fracture based modeling tools that thermodynamic predictions and inputs to predict concrete service life. These results have been used to demonstrate the value of enabling specifications to include ASTM C 595 cement as well ASTM C150 cement. In addition, these products are being used to expedite the evaluation of alternative SCM to aide in determining which materials have potential value and what ‘compositions’ of blended cements merit further investment.

42 ENGINEERING↗

In Situ Electrochemistry of Buried Interfaces in Metal Halide Perovskites: Probing Energy Bands, Halide Redox Activity, and Kinetics

Control over charge injection and extraction processes across buried interfaces is fundamental for all (opto)electronic multilayer device platforms, necessitating detailed understanding of local structural and chemical differences that promote defect formation, distort energetic band-edge alignments, and alter charge transport processes. Herein, the implementation of a low-cost electroanalytical methodologies’ tool suite is described to quantitatively characterize buried interfaces and redox reactions in printable, mixed electrical–ionic, and redox-active metal halide perovskites and a prototypical hole-transporting nickel oxide (NiO x ) thin film. The objective is to demonstrate the power of electrochemical methodologies to improve the nanoscale understanding of complex interfaces within optoelectronic devices by providing case studies on how to: i) differentiate between electronic and chemical properties in NiO x contacts; ii) measure changes in reversibility of halide redox reactions via NiO x surface states; iii) assess energy alignment and charge transport across (modified) buried interfaces; and iv) quantify defects at buried interfaces that change with modifiers and differences in perovskite processing, including increasing defect concentrations when films are slot-die-coated versus spin-cast. The collective approach addresses major challenges in understanding the precise energy landscape and interface reactivity under relevant electric fields that mimic operando conditions (away from equilibrium) and across length scales in thin film device formats.

(spectro)electrochemistry↗

A small molecule antagonizes jasmonic acid perception and auxin responses in vascular and nonvascular plants

The phytohormone jasmonoyl-L-isoleucine (JA-Ile) regulates many stress responses and developmental processes in plants. A co-receptor complex formed by the F-box protein Coronatine Insensitive 1 (COI1) and a Jasmonate (JA) ZIM-domain (JAZ) repressor perceives the hormone. JA-Ile antagonists are invaluable tools for exploring the role of JA-Ile in specific tissues and developmental stages, and for identifying regulatory processes of the signaling pathway. Using two complementary chemical screens, we identified three compounds that exhibit a robust inhibitory effect on both the hormone-mediated COI–JAZ interaction and degradation of JAZ1 and JAZ9 in vivo. One molecule, J4, also restrains specific JA-induced physiological responses in different angiosperm plants, including JA-mediated gene expression, growth inhibition, chlorophyll degradation, and anthocyanin accumulation. Interaction experiments with purified proteins indicate that J4 directly interferes with the formation of the Arabidopsis (Arabidopsis thaliana) COI1–JAZ complex otherwise induced by JA. The antagonistic effect of J4 on COI1–JAZ also occurs in the liverwort Marchantia polymorpha, suggesting the mode of action is conserved in land plants. Besides JA signaling, J4 works as an antagonist of the closely related auxin signaling pathway, preventing Transport Inhibitor Response1/Aux–indole-3-acetic acid interaction and auxin responses in planta, including hormone-mediated degradation of an auxin repressor, gene expression, and gravitropic response. However, J4 does not affect other hormonal pathways. Altogether, our results show that this dual antagonist competes with JA-Ile and auxin, preventing the formation of phylogenetically related receptor complexes. J4 may be a useful tool to dissect both the JA-Ile and auxin pathways in particular tissues and developmental stages since it reversibly inhibits these pathways. One-sentence summary: A chemical screen identified a molecule that antagonizes jasmonate perception by directly interfering with receptor complex formation in phylogenetically distant vascular and nonvascular plants.

59 BASIC BIOLOGICAL SCIENCES↗

Reinspection of a Clinical Proteomics Tumor Analysis Consortium (CPTAC) Dataset with Cloud Computing Reveals Abundant Post-Translational Modifications and Protein Sequence Variants

The Clinical Proteomic Tumor Analysis Consortium (CPTAC) has provided some of the most in-depth analyses of the phenotypes of human tumors ever constructed. Today, the majority of proteomic data analysis is still performed using software housed on desktop computers which limits the number of sequence variants and post-translational modifications that can be considered. The original CPTAC studies limited the search for PTMs to only samples that were chemically enriched for those modified peptides. Similarly, the only sequence variants considered were those with strong evidence at the exon or transcript level. In this multi-institutional collaborative reanalysis, we utilized unbiased protein databases containing millions of human sequence variants in conjunction with hundreds of common post-translational modifications. Using these tools, we identified tens of thousands of high-confidence PTMs and sequence variants. We identified 4132 phosphorylated peptides in nonenriched samples, 93% of which were confirmed in the samples which were chemically enriched for phosphopeptides. In addition, our results also cover 90% of the high-confidence variants reported by the original proteogenomics study, without the need for sample specific next-generation sequencing. Finally, we report fivefold more somatic and germline variants that have an independent evidence at the peptide level, including mutations in ERRB2 and BCAS1. In this reanalysis of CPTAC proteomic data with cloud computing, we present an openly available and searchable web resource of the highest-coverage proteomic profiling of human tumors described to date.

60 APPLIED LIFE SCIENCES↗

Low thrust chemical rocket technology

An on-going technology program to improve the performance of low thrust chemical rockets for spacecraft on-board propulsion applications is reviewed. Improved performance and lifetime is sought by the development of new predictive tools to understand the combustion and flow physics, introduction of high temperature materials and improved component designs to optimize performance, and use of higher performance propellants. Improved predictive technology is sought through the comparison of both local and global predictions with experimental data. Predictions are based on both the RPLUS Navier-Stokes code with finite rate kinetics and the JANNAF methodology. Data were obtained with laser-based diagnostics along with global performance measurements. Results indicate that the modeling of the injector and the combustion process needs improvement in these codes and flow visualization with a technique such as 2-D laser induced fluorescence (LIF) would aid in resolving issues of flow symmetry and shear layer combustion processes. High temperature material fabrication processes are under development and small rockets are being designed, fabricated, and tested using these new materials. Rhenium coated with iridium for oxidation protection was produced by the Chemical Vapor Deposition (CVD) process and enabled an 800 K increase in rocket operating temperature. Performance gains with this material in rockets using Earth storable propellants (nitrogen tetroxide and monomethylhydrazine or hydrazine) were obtained through component redesign to eliminate fuel film cooling and its associated combustion inefficiency while managing head end thermal soakback. Material interdiffusion and oxidation characteristics indicated that the requisite lifetimes of tens of hours were available for thruster applications. Rockets were designed, fabricated, and tested with thrusts of 22, 62, 440 and 550 N. Performance improvements of 10 to 20 seconds specific impulse were demonstrated. Higher performance propellants were evaluated: Space storable propellants, including liquid oxygen (LOX) as the oxidizer with nitrogen hydrides or hydrocarbon as fuels. Specifically, a LOX/hydrazine engine was designed, fabricated, and shown to have a 95 pct theoretical c-star which translates into a projected vacuum specific impulse of 345 seconds at an area ratio of 204:1. Further performance improvment can be obtained by the use of LOX/hydrogen propellants, especially for manned spacecraft applications, and specific designs must be developed and advanced through flight qualification.

Schneider, Steven J.↗

Editorial overview: Unlocking the secrets of nongenetic plasticity, one cell at a time

Cellular noise, the non-genetic variability observed among isogenic cells, arises from factors such as growth conditions, aging, and stochastic gene expression, influencing cell stress-response, metabolism, morphology, and size. Here, such plasticity, while critical for adaptation, often goes unnoticed with traditional population-averaging biotechnologies that inevitably mask cell-specific variations and prompting the question, "What else might we be missing". However, recent breakthroughs in optical imaging, microfluidics, and omics, are beginning to uncover the complexity of cellular plasticity. This special is-sue highlights some of these breakthroughs, with key contributions including innovations in multimodal chemical imaging, label-free microscopy, spatial and temporal omics, and droplet-based microfluidics. Collectively, these cutting-edge tools provide unprecedent-ed insights into non-genetic cell-to-cell variability, enhancing our understanding of cellu-lar plasticity and its implications for health, energy, and ecology.

59 BASIC BIOLOGICAL SCIENCES↗

Isotopic Heterogeneity Imaged in a Uranium Fuel Pellet with Extreme Ultraviolet Laser Ablation and Ionization Time-of-Flight Mass Spectrometry

We use extreme ultraviolet laser ablation and ionization time-of-flight mass spectrometry (EUV TOF) to map uranium isotopic heterogeneity at the nanoscale (=100 nm). Using low-enriched uranium fuel pellets that were made by blending two isotopically distinct feedstocks, we show that EUV TOF can map the 235U/238U content in 100 nm-sized pixels. The two-dimensional (2D) isotope maps reveal U ratio variations in sub-microscale to =1 µm areas of the pellet that had not been fully exposed by microscale or bulk mass spectrometry analyses. Compared to the ratio distribution measured in a homogeneous U reference material, the ratios in the enriched pellet follow a ~3× wider distribution. These results indicate U heterogeneity in the fuel pellet from incomplete blending of the different source materials. EUV TOF results agree well with those obtained on the same enriched pellets by nanoscale secondary ionization mass spectrometry (NanoSIMS), which reveals a comparable U isotope ratio distribution at the same spatial scale. EUV TOF’s ability to assess and map isotopic heterogeneity at the nanoscale makes it a promising tool in fields such as nuclear forensics, geochemistry, and biology that could benefit from uncovering sub-microscale sources of chemical modifications.

Rush, Lydia A.↗

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

We report that Redox flow batteries (RFBs) are promising devices for grid-scale energy storage due to the decoupling of power and energy, which can be independently scaled by the electrode area and storage tank size, respectively. To date, only aqueous RFBs, such as the vanadium RFB, have been implemented commercially. Nevertheless, the limited energy densities and high-cost materials may preclude their wider market penetration. Organic non-aqueous redox-flow batteries (O-NRFBs), which utilize redox-active organic molecules (ROMs), have been offered as an attractive alternative. Many possible advantages include the use of earth-abundant elements (C, H, N, O, S, F), wherein the ROMs can be prepared from low-cost and sustainable materials. Additionally, a large variety of electroactive moieties are accessible as building blocks, providing a synthetic platform to tune the properties of ROMs through rational design. As a consequence, the development of novel ROMs has attracted researchers with diverse backgrounds, prompting remarkable innovations in the past decade. However, consistency in experimental protocols (e.g., electrochemical methods, cycling stability, experimental conditions) has not coincided with this uptick in research, leading to sometimes ambiguous and incomparable results. This is further convoluted by the complexity innate to battery development, such as cell design, detection, and characterization of reactions and active components. The O-NRFB application imposes stringent requirements on the physical or/and chemical processes involved in electrochemical cycling. Yet such considerations are often overlooked. Further, while quantum mechanical calculations provide a convenient tool for evaluating and selecting ROM candidates, this simulation is not always performed. Thus, in this Energy Focus, we detail a means to standardize experimental protocols for studies of O-NRFBs and suggest practices to facilitate fundamental understanding and development of ROMs.

25 ENERGY STORAGE↗

X-ray near-field multi-slice ptychography for in-situ imaging

Abstract In-situ imaging of chemical reactions can provide valuable insight into nanoparticle growth and structural evolution. Hard X-ray imaging is an excellent tool for this purpose, as it combines high spatial resolution with high penetration depth, allowing for realistic reaction environments. While far-field ptychography is a well-established method at synchrotron radiation sources, its near-field analog has received less attention. In this work we show that near-field multi-slice ptychography is a competitive method for high-resolution in-situ imaging by studying the formation of gold nanocages via galvanic replacement. Our work extends near-field X-ray ptychography to sub-50 nm spatial resolution by using multilayer Laue lenses. These high numerical aperture optics enable to distinguish sample layers that are separated by less than 100 µm by multi-slicing techniques.

Science & Technology - Other Topics↗

Solar fuels and feedstocks: the quest for renewable black gold

Photocatalysis for organic synthesis is a tool capable of C–C, C–O and C–N bond transformations. This technology has the potential to transform the chemical manufacturing industry and support growing demand for chemical feedstocks. Compared to traditional catalysis, photocatalysis can access alternative reaction pathways that lower the overall energy requirement and operate at or near ambient conditions. A key challenge is the delivery of photoenergy at the scale required for rapid and efficient operation of the catalyst. The development of efficient, broad-spectrum light harvesting devices that funnel light energy to a catalyst, along with catalyst design to selectively enable high-energy reactions, are necessary steps towards solar fuels and feedstocks. Furthermore, this perspective highlights some recent advances in photocatalysis and advocates for expanding the scope of photocatalysis for large-scale industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regulating off-centering distortion maximizes photoluminescence in halide perovskites

Abstract Metal halide perovskites possess unique atomic and electronic configurations that endow them with high defect tolerance and enable high-performance photovoltaics and optoelectronics. Perovskite light-emitting diodes have achieved an external quantum efficiency of over 20%. Despite tremendous progress, fundamental questions remain, such as how structural distortion affects the optical properties. Addressing their relationships is considerably challenging due to the scarcity of effective diagnostic tools during structural and property tuning as well as the limited tunability achievable by conventional methods. Here, using pressure and chemical methods to regulate the metal off-centering distortion, we demonstrate the giant tunability of photoluminescence (PL) in both the intensity (>20 times) and wavelength (>180 nm/GPa) in the highly distorted halide perovskites [CH3NH3GeI3, HC(NH2)2GeI3, and CsGeI3]. Using advanced in situ high-pressure probes and first-principles calculations, we quantitatively reveal a universal relationship whereby regulating the level of off-centering distortion towards 0.2 leads to the best PL performance in the halide perovskites. By applying this principle, intense PL can still be induced by substituting CH3NH3+ with Cs+ to control the distortion in (CH3NH3)1-xCsxGeI3, where the chemical substitution plays a similar role as external pressure. The compression of a fully substituted sample of CsGeI3 further tunes the distortion to the optimal value at 0.7 GPa, which maximizes the emission with a 10-fold enhancement. This work not only demonstrates a quantitative relationship between structural distortion and PL property of the halide perovskites but also illustrates the use of knowledge gained from high-pressure research to achieve the desired properties by ambient methods.

halide perovskites↗

Mass spectral imaging showing the plant growth-promoting rhizobacteria's effect on the Brachypodium awn

The plant growth-promoting rhizobacteria (PGPR) on the host plant surface play a key role in biological control and pathogenic response in plant functions and growth. However, it is difficult to elucidate the PGPR effect on plants. Such information is important in biomass production and conversion. Brachypodium distachyon (Brachypodium), a genomics model for bioenergy and native grasses, was selected as a C3 plant model; and the Gram-negative Pseudomonas fluorescens SBW25 ( P.) and Gram-positive Arthrobacter chlorophenolicus A6 ( A.) were chosen as representative PGPR strains. The PGPRs were introduced to the Brachypodium seed's awn prior to germination, and their possible effects on the seeding and growth were studied using different modes of time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements, including a high mass-resolution spectral collection and delayed image extraction. We observed key plant metabolic products and biomarkers, such as flavonoids, phenolic compounds, fatty acids, and auxin indole-3-acetic acid in the Brachypodium awns. Furthermore, principal component analysis and two-dimensional imaging analysis reveal that the Brachypodium awns are sensitive to the PGPR, leading to chemical composition and morphology changes on the awn surface. Our results show that ToF-SIMS can be an effective tool to probe cell-to-cell interactions at the biointerface. This work provides a new approach to studying the PGPR effects on awn and shows its potential for the research of plant growth in the future.

metabolite↗

Nondestructive spot tests allow rapid identification of metals

Ordered qualitative test sequence, presented in flow chart form, permits identification of all common metallurgical elements and many high-temperature, stainless, high and low carbon, and tool steels within about 30 minutes. Identification is made from colors or specific reactions produced by the addition of standard chemical reagents.

Wilson, M. L.↗

Developments in flow visualization methods for flight research

With the introduction of modern airplanes utilizing laminar flow, flow visualization has become an important diagnostic tool in determining aerodynamic characteristics such as surface flow direction and boundary-layer state. A refinement of the sublimating chemical technique has been developed to define both the boundary-layer transition location and the transition mode. In response to the need for flow visualization at subsonic and transonic speeds and altitudes above 20,000 feet, the liquid crystal technique has been developed. A third flow visualization technique that has been used is infrared imaging, which offers non-intrusive testing over a wide range of test conditions. A review of these flow visualization methods and recent flight results is presented for a variety of modern aircraft and flight conditions.

Holmes, Bruce J.↗

The Life Support Database system

The design and implementation of the database system are described with specific reference to data available from the Build-1 version and techniques for its utilization. The review of the initial documents for the Life Support Database is described in terms of title format and sequencing, and the users are defined as participants in NASA-sponsored life-support research. The software and hardware selections are based respectively on referential integrity and compatibility, and the implementation of the user interface is achieved by means of an applications-programming tool. The current Beta-Test implementation of the system includes several thousand acronyms and bibliographic references as well as chemical properties and exposure limits, equipment, construction materials, and mission data. In spite of modifications in the database the system is found to be effective and a potentially significant resource for the aerospace community.

Likens, William C.↗

Chemical Modification of Nanotubes for Composites

In the production of mesoscopically-engineered materials based on single-walled carbon nanotubes (SWNTs), monitoring the stages of chemical modification will be an important step in the fabrication of usable composite materials. In our research program we developed tools for studying high-temperature composites with a long-term goal of having such instrumentation available for SWNT composite analyses.

Samulski, Edward T.↗