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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

Singlet Oxygen Leads to Structural Changes to Chloroplasts during their Degradation in the Arabidopsis thaliana plastid ferrochelatase two Mutant

Abstract During stress, chloroplasts produce large amounts of reactive oxygen species (ROS). Chloroplasts also contain many nutrients, including 80% of a leaf’s nitrogen supply. Therefore, to protect cells from photo-oxidative damage and to redistribute nutrients to sink tissues, chloroplasts are prime targets for degradation. Multiple chloroplast degradation pathways are induced by photo-oxidative stress or nutrient starvation, but the mechanisms by which damaged or senescing chloroplasts are identified, transported to the central vacuole and degraded are poorly defined. Here, we investigated the structures involved with degrading chloroplasts induced by the ROS singlet oxygen (1O2) in the Arabidopsis thaliana plastid ferrochelatase two (fc2) mutant. Under mild 1O2 stress, most fc2 chloroplasts appeared normal, but had reduced starch content. A subset of chloroplasts was degrading, and some protruded into the central vacuole via ‘blebbing’ structures. A 3D electron microscopy analysis demonstrated that up to 35% of degrading chloroplasts contained such structures. While the location of a chloroplast within a cell did not affect the likelihood of its degradation, chloroplasts in spongy mesophyll cells were degraded at a higher rate than those in palisade mesophyll cells. To determine if degrading chloroplasts have unique structural characteristics, allowing them to be distinguished from healthy chloroplasts, we analyzed fc2 seedlings grown under different levels of photo-oxidative stress. A correlation was observed among chloroplast swelling, 1O2 signaling and the state of degradation. Finally, plastoglobule (PG) enzymes involved in chloroplast disassembly were upregulated while PGs increased their association with the thylakoid grana, implicating an interaction between 1O2-induced chloroplast degradation and senescence pathways.

59 BASIC BIOLOGICAL SCIENCES↗

Compartmental Control of UDP-Araf Supply: Golgi Lumen UDP-Arabinopyranose Mutase Depletes Plant Cell Wall Araf Linkages

L-Arabinofuranose (Araf) is a major constituent of plant cell wall polysaccharides. UDP-Araf is generated from UDP-L-arabinopyranose (UDP-Arap) by a UDP-Arap mutase (UAM) on the cytosolic face of the Golgi and then imported into the Golgi lumen for utilization by arabinosyltransferases (AraTs). Yet, a substantial fraction of UDP-Arap is synthesized in the Golgi lumen by the UDP-xylose 4-epimerase (UXE), creating a topological paradox where luminal UDP-Arap must be exported to the cytosol for conversion to UDP-Araf by UAM and then re-imported into the Golgi lumen. To test the functional significance of this compartmentation, we mislocalized Arabidopsis (Arabidopsis thaliana) UAM1 to the Golgi lumen by fusing it to the UXE1 transmembrane domain. The fusion protein was present in the Golgi, and protease-protection assays on microsomes supported its luminal orientation. In wild-type and uam1 plants, Golgi-targeted UAM1 reduced total cell wall Arabinose without consistent changes in other monosaccharides. Linkage analyses showed that this decrease reflects selective loss of Araf residues, whereas Arap remain largely unchanged, consistent with reduced UDP-Araf availability for luminal AraTs. Under salt stress, expression of Golgi-targeted UAM1 in uam1 caused root-growth inhibition and maturation-zone swelling that exogenous L-Ara failed to rescue. These results support a hypothesis that the strong thermodynamic bias of the UAM reaction toward UDP-Arap requires spatial separation of UDP-Arap production from UDP-Araf formation to sustain UDP-Araf flux into Golgi arabinosylation and avoid futile intraluminal back-conversion.

59 BASIC BIOLOGICAL SCIENCES↗

Dynamic structural and microstructural responses of a metal–organic framework type material to carbon dioxide under dual gas flow and supercritical conditions

The structural and microstructural responses of a model metal–organic framework material, Ni(3-methyl-4,4'-bipyridine)[Ni(CN) 4 ] (Ni-BpyMe or PICNIC-21), to CO 2 adsorption and desorption are reported for in situ small-angle X-ray scattering and X-ray diffraction measurements under different gas pressure conditions for two technologically important cases. These conditions are single or dual gas flow (CO 2 with N 2 , CH 4 or H 2 at sub-critical CO 2 partial pressures and ambient temperatures) and supercritical CO 2 (with static pressures and temperatures adjusted to explore the gas, liquid and supercritical fluid regimes on the CO 2 phase diagram). The experimental results are compared with density functional theory calculations that seek to predict where CO 2 and other gas molecules are accommodated within the sorbent structure as a function of gas pressure conditions, and hence the degree of swelling and contraction in the associated structure spacings and void spaces. Furthermore, these predictions illustrate the insights that can be gained concerning how such sorbents can be designed or modified to optimize the desired gas sorption properties relevant to enhanced gas recovery or to addressing carbon dioxide reduction through carbon mitigation, or even direct air capture of CO 2 .

36 MATERIALS SCIENCE↗

Oxidation performance and limitations of additively manufactured SiC/Si-O-C composites at elevated temperatures

Here, SiC preforms were infiltrated with polycarbosiloxane preceramic polymer to create low-cost SiC—Si x O y C z matrix composites for possible high temperature application. The effect of specimen annealing conditions on the steam and air oxidation resistance was analyzed. Air exposures from 900–1500°C showed stability of the Si x O y C z matrix phase with moderate oxidation resistance. After 900°C exposures, oxidation of the composite is primarily limited to the matrix phase, and only at 1200 and 1500°C was SiC consumption visualized. Steam cycle exposures at 1200°C resulted in rapid linear oxidation of the composites with induced specimen swelling from volume expansion associated with internal oxidation. Specimens annealed in argon were found to be the most oxidation resistant due to increased matrix crystallinity and carbon retention. The results of this work were used to develop clear strategies for improving the high-temperature properties of SiC—Si x O y C z composites.

36 MATERIALS SCIENCE↗

Lack of xyloglucan in the cell walls of the Arabidopsis xxt1/xxt2 mutant results in specific increases in homogalacturonan and glucomannan

Mutations in both ArabidopsisXyloglucan Xylosyltransferase1 (XXT1) and Xyloglucan Xylosyltransferase2 (XXT2) result in the absence of the major hemicellulose, xyloglucan (XyG). The growth physiology, tensile strength, and cell wall compositions of etiolated hypocotyls of xxt1/xxt2 double and xxt1/xxt2/xxt5 triple mutants were characterized and compared with those of mur2 and mur3 mutations that alter the side group composition of XyG. Wild type and mur2 demonstrated normal elongation growth, whereas the xxt double and triple mutants and mur3 showed reduced elongation and cell swelling at the base of the hypocotyl at the later stages of elongation. Whereas mur3 hypocotyls had reduced tensile strength, the xxt double and triple mutants had similar tensile strengths as wild type, but reached breaking points at lower strains. Loss of XyG in hypocotyls and rosette leaf cell walls was associated with specific increases in the relative abundance of homogalacturonan and the hemicellulose glucomannan, but not arabinoxylan. The increased homogalacturonan and glucomannan abundance did not result from enhanced expression of their polymer synthases. An analysis of published transcriptomic data indicated that genes encoding some members of the expansin, xyloglucan endotransglucosylase/hydrolase, arabinogalactan-protein, and structural protein families were upregulated in the xxt mutants. We hypothesize that an as yet unknown mechanism exists by which pectin and hemicellulose abundance can be altered other than by increased rates of biosynthesis to maintain a structurally sound cell wall.

59 BASIC BIOLOGICAL SCIENCES↗

Experimental Characterization of Hygrothermal Aging: Competition Between Thermo-Oxidation and Hydrolysis Phenomena

Abstract In this work, we have presented a comparison between effects of accelerated thermo-oxidative, hydrolytic and hygrothermal aging on the mechanical and chemical properties of a polyurethane based (PUB) adhesive. The adhesive is a flexible adhesive which is extensively used in automobile industry as a glass sealant. During service life it gets exposed to the hygrothermal environment and the integrity of matrix interface is most vulnerable. This study focuses on weighing and comparing effects of different aging environments on material behavior; and it shows that hygrothermal aging environment results as a competition between two sub-aging phenomena i.e., thermo-oxidation and hydrolytic aging. Samples were exposed to 0%RH, 80%RH and submerged condition in distilled water. Uni-axial tensile tests, and cross-link density analysis by swelling test were carried out on as-received and aged samples. The aging process was conducted at three different temperatures (60°C, 80°C and 95°C) and for four different exposure durations of 1, 10, 30, and 90 days. This work confirms that the effect of hygrothermal aging is a result of competition between thermo-oxidation and hydrolytic aging environments. The total mechanical and environmental damage incurred by specimens is a collaborative effect of all exposure environments involved i.e., aging time, temperature, oxygen, water and humidity. The results are in agreement with the chemical test outcomes as well.

Shaafaey, Mamoon↗

Topology control of human fibroblast cells monolayer by liquid crystal elastomer

Eukaryotic cells in living tissues form dynamic patterns with spatially varying orientational order that affects important physiological processes such as apoptosis and cell migration. The challenge is how to impart a predesigned map of orientational order onto a growing tissue. Here, we demonstrate an approach to produce cell monolayers of human dermal fibroblasts with predesigned orientational patterns and topological defects using a photoaligned liquid crystal elastomer (LCE) that swells anisotropically in an aqueous medium. The patterns inscribed into the LCE are replicated by the tissue monolayer and cause a strong spatial variation of cells phenotype, their surface density, and number density fluctuations. Unbinding dynamics of defect pairs intrinsic to active matter is suppressed by anisotropic surface anchoring allowing the estimation of the elastic characteristics of the tissues. The demonstrated patterned LCE approach has potential to control the collective behavior of cells in living tissues, cell differentiation, and tissue morphogenesis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic resonance insights into the heterogeneous, fractal-like kinetics of chemically recyclable polymers

Moving toward a circular plastics economy is a vital aspect of global resource management. Chemical recycling of plastics ensures that high-value monomers can be recovered from depolymerized plastic waste, thus enabling circular manufacturing. However, to increase chemical recycling throughput in materials recovery facilities, the present understanding of polymer transport, diffusion, swelling, and heterogeneous deconstruction kinetics must be systematized to allow industrial-scale process design, spanning molecular to macroscopic regimes. To develop a framework for designing depolymerization processes, we examined acidolysis of circular polydiketoenamine elastomers. We used magnetic resonance to monitor spatially resolved observables in situ and then evaluated these data with a fractal method that treats nonlinear depolymerization kinetics. This approach delineated the roles played by network architecture and reaction medium on depolymerization outcomes, yielding parameters that facilitate comparisons between bulk processes. These streamlined methods to investigate polymer hydrolysis kinetics portend a general strategy for implementing chemical recycling on an industrial scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanochemically accelerated deconstruction of chemically recyclable plastics

Plastics redesign for circularity has primarily focused on monomer chemistries enabling faster deconstruction rates concomitant with high monomer yields. Yet, during deconstruction, polymer chains interact with their reaction medium, which remains underexplored in polymer reactivity. Here, we show that, when plastics are deconstructed in reaction media that promote swelling, initial rates are accelerated by over sixfold beyond those in small-molecule analogs. This unexpected acceleration is primarily tied to mechanochemical activation of strained polymer chains; however, changes in the activity of water under polymer confinement and bond activation in solvent-separated ion pairs are also important. Together, deconstruction times can be shortened by seven times by codesigning plastics and their deconstruction processes.

36 MATERIALS SCIENCE↗

Decoding the interstitial/vacancy nature of dislocation loops with their morphological fingerprints in face-centered cubic structure

Dislocation loops are critical defects inducing detrimental effects like embrittlement and swelling in materials under irradiation. Distinguishing their nature (interstitial- or vacancy-type) is a long-standing challenge with great implications for understanding radiation damage. Here, we demonstrate that the morphology of radiation-induced Frank loops can unveil their nature in face-centered cubic (fcc) structure: Circular loops are interstitial-type in all fcc materials, while segmented loops are vacancy-type in high stacking fault energy (SFE) alloys but varied-type in low SFE and high-entropy alloys. The polygonal shape is attributed to the dissociation of an a 0 /3<111> dislocation into an a 0 /6<112> Shockley partial and an a 0 /6<110> stair-rod dislocation. The dissociation of vacancy loops is energetically favorable, whereas interstitial loops require external stimuli to promote dislocation propagation. This “morphology-nature” correlation not only highlights the asymmetry of vacancy/interstitial loops but also offers an efficient way to distinguish loop nature for a wide range of materials.

Ma, Kan [City Univ. of Hong Kong, Kowloon (Hong Ko↗

Shoreline wave breaking strongly enhances the coastal sea spray aerosol population: Climate and air quality implications

Sea spray aerosol (SSA) emission is a major source of atmospheric aerosols, influencing global climate and coastal air quality. Much of our knowledge about SSA derives from coastal observations near shorelines, but whether and when these observations accurately represent open oceans remain unclear. Here, we show that strong nearshore SSA production during high-wave periods greatly enhances downwind cloud condensation nuclei (CCN) and aerosol mass concentrations. Strong shoreline wave breaking is widespread globally, and swell waves, which are decoupled from local winds, play a dominant role in many coastal regions. Therefore, extrapolating results based on coastal measurements to open oceans may significantly overestimate SSA concentration and its contribution to CCN and, by extension, the impact of SSA on clouds and climate. Additionally, the strong enhancement of coastal aerosol population by shoreline wave breaking and its environmental impact on coastal communities cannot be captured by current regional models, which do not parameterize nearshore SSA generation using wave energy or completely neglect it.

54 ENVIRONMENTAL SCIENCES↗

Mapping structures and dynamics with frequency-correlated diffusion exchange

Understanding molecular motion in diffusion-driven complex environments is critical for designing sustainable materials and improving chemical processes. Here, we introduce a multidimensional nuclear magnetic resonance (NMR) method that captures how molecular populations exchange across different dynamic regimes. By extending the modulated gradient spin-echo technique to include frequency-frequency correlations, our approach reveals diffusion pathways that are otherwise obscured in heterogeneous systems. Implemented on a unilateral NMR magnet, the method eliminates gradient pulsing constraints and accesses dynamics in the kilohertz regime. We apply this technique to swelling and acid-catalyzed deconstruction of cross-linked and linear polymers to observe how structural heterogeneity evolves over time. By linking molecular motion to topology and chemical state, we extract physical metrics such as fractal surface dimensionality and reaction wavefront velocity, properties inaccessible with standard diffusion measurements. This work expands the capabilities of NMR for probing soft matter, with implications for polymer recycling and materials design.

Fricke, Sophia N. [University of California, Berke↗

Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes

The plasticization of a polymer electrolyte usually promotes its ionic conductivity but decreases its storage modulus due to the increased polymer chain flexibility. Herein, we show that such a tradeoff between the ionic conductivity and the mechanical robustness of the polymer electrolyte can be alleviated by selective plasticization of the ion-conductive block, such as poly(ethylene oxide) (PEO) in a polystyrene (PS)– PEO–PS block copolymer (SEO) electrolyte using an ether type plasticizer, tetraethylene glycol dimethyl ether (TEGDME). In this work, at maximum plasticizer loading, the room temperature ionic conductivity increases by up to 3 orders, whereas the storage modulus, G' reduces to half, is still on the order of 10 2 MPa. At above the melting temperature of the PEO block, the dynamic storage modulus, G' of the plasticized membrane surpasses its dry PS-PEO-PS counterpart. Such a phenomenon results from that, a) TEGDME co-crystallizes with PEO to promote its crystallinity and hence the storage modulus, b) TEGDME swells the amorphous PEO phase to enhance the polymer chain segmental mobility and hence ionic conductivity, and c) the PS phase remains intact from TEGDME to keep the SEO elastic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved Fuel Cell Chemical Durability of an Heteropoly Acid Functionalized Perfluorinated Terpolymer-Perfluorosulfonic Acid Composite Membrane

Commercial proton exchange membrane heavy-duty fuel cell vehicles will require a five-fold increase in durability compared to current state-of-the art light-duty fuel cell vehicles. We describe a new composite membrane that incorporates silicotungstic heteroply acid (HPA), α -K 8 SiW 11 O 40 ▪13H 2 O, a radical decomposition catalyst and when acid-exchanged can potentially conduct protons. The HPA was covalently bound to a terpolymer of tetrafluoroethylene, vinylidene fluoride, and sulfonyl fluoride containing monomer (1,1,2,2,3,3,4,4-octafluoro-4-((1,2,2-trifluorovinyl)oxy)butane-1-sulfonyl fluoride) by dehydrofluorination followed by addition of diethyl (4-hydroxyphenyl) phosphonate, giving a perfluorosulfonic acid-vinylidene fluoride-heteropoly acid (PFSA-VDF-HPA). A composite membrane was fabricated using a blend of the PFSA-VDF-HPA and the 800EW 3M perfluoro sulfonic acid polymer. The bottom liner-side of the membrane tended to have a higher proportion of HPA moieties compared to the air-side as gravity caused the higher mass density PFSA-VDF-HPA to settle. The composite membrane was shown to have less swelling, more hydrophobic properties, and higher crystallinity than the pure PFSA membrane. The proton conductivity of the membrane was 0.130 ± 0.03 S cm −1 at 80 °C and 95% RH. Impressively, when the membrane with HPA-rich side was facing the anode, the membrane survived more than 800 h under accelerated stress test conditions of open-circuit voltage, 90 °C and 30% RH.

08 HYDROGEN↗

Modeling Sorption of Water and Vanadium Cations by Ion-Exchange Membranes

We develop a macroscopic model for sorption of ions and solvent by ion-exchange membranes and use it to investigate how different membranes behave when exposed to electrolytes for vanadium flow batteries. The model combines a classical expression for the Gibbs free energy of a moderately concentrated electrolyte containing several ions with a term that describes elastic swelling of a polymer membrane. Parameters describing pairwise interactions between mobile ions and fixed membrane ions were fit to published experimental data and discussed in the context of the competition for sites in ion-exchange membranes. The model provides insights into why sorption of vanadium cations by Nafion is lower than predicted by Donnan theory and why switching to an anion-exchange membrane does not dramatically reduce vanadium sorption.

Electrochemistry↗

GOOSE (GRAPHITE OBJECT-ORIENTED SIMULATION ENVIRONMENT)

This package is a set of extensions to MOOSE (https://moose.inl.gov) adding anisotropic graphite material models for irradiation creep and swelling. The goal of the package is to provide a framework to model graphite components for use in future high temperature nuclear reactors.

MESSNER, MARKCHRISTIAN↗

The Extraordinary March 2022 East Antarctica “Heat” Wave. Part II: Impacts on the Antarctic Ice Sheet

Abstract Between 15 and 19 March 2022, East Antarctica experienced an exceptional heat wave with widespread 30°–40°C temperature anomalies across the ice sheet. In Part I, we assessed the meteorological drivers that generated an intense atmospheric river (AR) that caused these record-shattering temperature anomalies. Here, we continue our large collaborative study by analyzing the widespread and diverse impacts driven by the AR landfall. These impacts included widespread rain and surface melt that was recorded along coastal areas, but this was outweighed by widespread high snowfall accumulations resulting in a largely positive surface mass balance contribution to the East Antarctic region. An analysis of the surface energy budget indicated that widespread downward longwave radiation anomalies caused by large cloud-liquid water contents along with some scattered solar radiation produced intense surface warming. Isotope measurements of the moisture were highly elevated, likely imprinting a strong signal for past climate reconstructions. The AR event attenuated cosmic ray measurements at Concordia, something previously never observed. Last, an extratropical cyclone west of the AR landfall likely triggered the final collapse of the critically unstable Conger Ice Shelf while further reducing an already record low sea ice extent. Significance Statement Using our diverse collective expertise, we explored the impacts from the March 2022 heat wave and atmospheric river across East Antarctica. One key takeaway is that the Antarctic cryosphere is highly sensitive to meteorological extremes originating from the midlatitudes and subtropics. Despite the large positive temperature anomalies driven from strong downward longwave radiation, this event led to huge amounts of snowfall across the Antarctic interior desert. The isotopes in this snow of warm airmass origin will likely be detectable in future ice cores and potentially distort past climate reconstructions. Even measurements of space activity were affected. Also, the swells generated from this storm helped to trigger the final collapse of an already critically unstable Conger Ice Shelf while further degrading sea ice coverage.

Wille, Jonathan D.↗