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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 181 records · Page 10

Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy

High-capacity Ni-rich layered oxides are promising cathode materials for secondary lithium-based battery systems. However, their structural instability detrimentally affects the battery performance during cell cycling. Here, we report an Al/Zr co-doped single-crystalline LiNi<:sub>0.88 Co 0.09 Mn 0.03 O 2 (SNCM) cathode material to circumvent the instability issue. We found that soluble Al ions are adequately incorporated in the SNCM lattice while the less soluble Zr ions are prone to aggregate in the outer SNCM surface layer. The synergistic effect of Al/Zr co-doping in SNCM lattice improve the Li-ion mobility, relief the internal strain, and suppress the Li/Ni cation mixing upon cycling at high cut-off voltage. These features improve the cathode rate capability and structural stabilization during prolonged cell cycling. In particular, the Zr-rich surface enables the formation of stable cathode-electrolyte interphase, which prevent SNCM from unwanted reactions with the non-aqueous fluorinated liquid electrolyte solution and avoid Ni dissolution. To prove the practical application of the Al/Zr co-doped SNCM, we assembled a 10.8 Ah pouch cell (using a 100 μm thick Li metal anode) capable of delivering initial specific energy of 504.5 Wh kg- 1 at 0.1 °C and 25 °C.

25 ENERGY STORAGE↗

Effects of Ink Formulation on Construction of Catalyst Layers for High-Performance Polymer Electrolyte Membrane Fuel Cells

Rational design of catalyst layers in a membrane electrode assembly (MEA) is crucial for achieving high-performance polymer electrolyte membrane fuel cells. Establishing a clear understanding of the property (catalyst ink)–structure (catalyst layer)–performance (MEA) relationship lays the foundation for this rational design. Here, a synergistic approach was taken to correlate the ink formulation, the microstructure of catalyst layers, and the resulting MEA performance to establish such a property–structure–performance relationship. The solvent composition (n-PA/H 2 O mixtures) demonstrated a strong influence on the performance of the MEA fabricated with an 830-EW (Aquivion) ionomer, especially polarization losses of cell activation and mass transport. The performance differences were studied in terms of how the solvent composition affects the catalyst/ionomer interface, ionomer network, and pore structure of the resulting catalyst layers. The ionomer aggregates mainly covered the surface of catalyst aggregates acting as oxygen reduction reaction active sites, and the aggregate sizes of the ionomer and catalyst (revealed by ultrasmall angle X-ray scattering and cryo-transmission electron microscopy) were dictated by tuning the solvent composition, which in turn determined the catalyst/ionomer interface (available active sites). In n-PA/H 2 O mixtures with 50~90 wt % H 2 O, the catalyst agglomerates could be effectively broken up into small aggregates, leading to enhanced kinetic activities. The boiling point of the mixed solvents determined the pore structure of ultimate catalyst layers, as evidenced by mercury porosimetry and scanning electron microscopy. For mixed solvents with a higher boiling point, the catalyst–ionomer aggregates in the ink tend to agglomerate during the solvent evaporation process and finally form larger catalyst–ionomer aggregates in the ultimate catalyst layer, resulting in more secondary pores and thus lower mass transport resistance. Both the enlarged catalyst/ionomer interface and appropriate pore structure were achieved with the catalyst layer fabricated from an n-PA/H 2 O mixture with 90 wt % H 2 O, leading to the best MEA performance.

25 ENERGY STORAGE↗

Molecular Tuning of Ether Cosolvent Chemistry for High-Voltage Sodium-Ion Batteries

Ethers as electrolyte cosolvents in sodium-ion batteries (SIBs) provide favorable Na + solvation and interfacial properties, but their low oxidative stability limits their use in high-voltage SIBs. Herein, we address this limitation via molecular tuning of ether cosolvents for high-voltage (4.2 V) hard carbon || NaNi 0.33 Fe 0.33 Mn 0.33 O 2 full cells. Tetrahydropyran (THP) is functionalized with a nitrile group to form tetrahydropyran-4-carbonitrile (THPCN). To delineate the effect of nitrile functionalization and benchmark ether against a conventional carbonate, THP, THPCN, and diethyl carbonate (DEC) are evaluated as cosolvents with ethylene carbonate. Nitrile functionalization lowers the HOMO energy of the ether, extends the electrolyte stability window, and alters Na⁺ solvation. Spectroscopic techniques and molecular dynamics simulations reveal that THPCN exhibits predominantly aggregate-dominated solvation (95.1 %) with weakened Na + -solvent interactions, producing the most anion-rich environment relative to DEC and THP cosolvents. THPCN-modified solvation promotes the formation of highly conductive, fluorine-enriched interphases that suppress parasitic reactions. Pouch full cells with THPCN sustained ~ 600 cycles at 4.2 V, outperforming THP and DEC. Operando gas analysis reveals that THPCN reduces CO 2 generation by 45% and H 2 generation by 30% relative to THP. Furthermore, the findings demonstrate nitrile functionalization as a molecular design strategy to stabilize ethers and enable high-voltage SIBs.

25 ENERGY STORAGE↗

Radiation-induced Alteration of Meta-chert

Concrete aggregate identified as “meta-chert” was irradiated with gamma-rays and neutrons. To identify the volume expansion of the aggregate under neutron irradiation, herein the following analyses were performed for pristine and irradiated α-quartz and meta-chert: X-ray diffraction (XRD)/Rietveld analysis, dimension change, water pycnometry, He-pycnometry, light optical microscopy (LOM), and scanning electron microscopy (SEM). From the difference of volume expansion observed from dimension change and water / helium pycnometry, the crack opening inside the aggregate subjected to irradiation was elucidated, and this was confirmed by LOM and SEM analysis. The crack contribution to the expansion of the aggregate was significant for neutron fluence > 6.99 × 1019 n/cm 2 , for E ≥ 0.01 MeV. Based on the XRD analysis, changes in lattice parameters were identified and the cell volume expansion was compared with the data by helium pycnometry. Based on the density change calculation and phase calculation data, the density of X-ray amorphous phase was consistent with that of expanded crystal α-quartz.

36 MATERIALS SCIENCE↗

Electronic landscape of the f -electron intermetallics with the ThCr 2 Si 2 structure

Although strongly correlated f -electron systems are well known as reservoirs for quantum phenomena, a persistent challenge is to design specific states. What is often missing are simple ways to determine whether a given compound can be expected to exhibit certain behaviors and what tuning vector(s) would be useful to select the ground state. In this review, we address this question by aggregating information about Ce, Eu, Yb, and U compounds with the ThCr 2 Si 2 structure. We construct electronic/magnetic state maps that are parameterized in terms of unit cell volumes and d -shell filling, which reveals useful trends including that (i) the magnetic and nonmagnetic examples are well separated, and (ii) the crossover regions harbor the examples with exotic states. These insights are used to propose structural/chemical regions of interest in these and related materials, with the goal of accelerating discovery of the next generation of f -electron quantum materials.

42 ENGINEERING↗

Engineering an efficient and bright split Corynactis californica green fluorescent protein

Split green fluorescent protein (GFP) has been used in a panoply of cellular biology applications to study protein translocation, monitor protein solubility and aggregation, detect protein–protein interactions, enhance protein crystallization, and even map neuron contacts. Recent work shows the utility of split fluorescent proteins for large scale labeling of proteins in cells using CRISPR, but sets of efficient split fluorescent proteins that do not cross-react are needed for multiplexing experiments. We present a new monomeric split green fluorescent protein (ccGFP) engineered from a tetrameric GFP found in Corynactis californica, a bright red colonial anthozoan similar to sea anemones and scleractinian stony corals. Split ccGFP from C. californica complements up to threefold faster compared to the original Aequorea victoria split GFP and enable multiplexed labeling with existing A. victoria split YFP and CFP.

59 BASIC BIOLOGICAL SCIENCES↗

A re-examination of the mechanism of whiting events: A new role for diatoms in Fayetteville Green Lake (New York, USA)

Whiting events—the episodic precipitation of fine-grained suspended calcium carbonates in the water column—have been documented across a variety of marine and lacustrine environments. Whitings likely are a major source of carbonate muds, a constituent of limestones, and important archives for geochemical proxies of Earth history. While several biological and physical mechanisms have been proposed to explain the onset of these precipitation events, no consensus has been reached thus far. Fayetteville Green Lake (New York, USA) is a meromictic lake that experiences annual whitings. Materials suspended in the water column collected through the whiting season were characterized using scanning electron microscopy and scanning transmission X-ray microscopy. Whitings in Fayetteville Green Lake are initiated in the spring within the top few meters of the water column, by precipitation of fine amorphous calcium carbonate (ACC) phases nucleating on microbial cells, as well as on abundant extracellular polymeric substances (EPS) frequently associated with centric diatoms. Whiting particles found in the summer consist of 5–7 μm calcite grains forming aggregates with diatoms and EPS. Simple calculations demonstrate that calcite particles continuously grow over several days, then sink quickly through the water column. In the late summer, partial calcium carbonate dissolution is observed deeper in the water column. Settling whiting particles, however, reach the bottom of the lake, where they form a major constituent of the sediment, along with diatom frustules. The role of diatoms and associated EPS acting as nucleation surfaces for calcium carbonates is described for the first time here as a potential mechanism participating in whitings at Fayetteville Green Lake. This mechanism may have been largely overlooked in other whiting events in modern and ancient environments.

54 ENVIRONMENTAL SCIENCES↗

Heat shock induces the nuclear accumulation of YAP1 via SRC

Highlights: • YAP1 enters the nucleus in response to heat shock. • YAP1 spontaneously returns to the cytoplasm after heat shock. • SRC is involved in the nuclear accumulation of YAP1. • HSP90 is involved in the return to the cytoplasm of YAP1. • YAP1 cross-talks with NF-κB signaling in response to heat shock. Yes-associated protein 1 (YAP1), a co-transcription activator, shuttles between the cytoplasm and the nucleus. Phosphorylation by large tumor suppressor kinases (LATS1/2) is the major determinant of YAP1 subcellular localization. Unphosphorylated YAP1 interacts with transcription factors in the nucleus and regulates gene transcription, while phosphorylated YAP1 is trapped in the cytoplasm and is degraded. We found that when U2OS and HeLa cells are exposed to 42 °C, YAP1 enters the nucleus within 30 min and returns to the cytoplasm at 4 h. SRC and HSP90 are involved in nuclear accumulation and return to the cytoplasm, respectively. Upon heat shock, LATS2 forms aggregates including protein phosphatase 1 and is dephosphorylated and inactivated. SRC activation is necessary for the formation of aggregates, while HSP90 is required for their dissociation. YAP1 is involved in heat shock-induced NF-κB signaling. Mechanistically, YAP1 is implicated in strengthening the interaction between RELA and DPF3, a component of SWI/SNF chromatin remodeling complex, in response to heat shock. Thus, YAP1 plays a role as a thermosensor.

60 APPLIED LIFE SCIENCES↗

Poly(vinyl alcohol) Hydrogels with Broad-Range Tunable Mechanical Properties via the Hofmeister Effect

Hydrogels, exhibiting wide applications in soft robotics, tissue engineering, implantable electronics, etc., often require sophisticately tailoring of the hydrogel mechanical properties to meet specific demands. For examples, soft robotics necessitates tough hydrogels; stem cell culturing demands various tissue-matching modulus; and neuron probes desire dynamically tunable modulus. Herein, a strategy to broadly alter the mechanical properties of hydrogels reversibly via tuning the aggregation states of the polymer chains by ions based on the Hofmeister effect is reported. An ultratough poly(vinyl alcohol) (PVA) hydrogel as an exemplary material (toughness 150 ± 20 MJ m -3 ), which surpasses synthetic polymers like poly(dimethylsiloxane), synthetic rubber, and natural spider silk is fabricated. With various ions, the hydrogel's various mechanical properties are continuously and reversibly in situ modulated over a large window: tensile strength from 50 ± 9 kPa to 15 ± 1 MPa, toughness from 0.0167 ± 0.003 to 150 ± 20 MJ m -3 , elongation from 300 ± 100% to 2100 ± 300%, and modulus from 24 ± 2 to 2500 ± 140 kPa. Importantly, the ions serve as gelation triggers and property modulators only, not necessarily required to remain in the gel, maintaining the high biocompatibility of PVA without excess ions. Overall, this strategy, enabling high mechanical performance and broad dynamic tunability, presents a universal platform for broad applications from biomedicine to wearable electronics.

36 MATERIALS SCIENCE↗

Harnessing Particle Size‐Control and DNA‐Oligo Functionalization in ZIF‐76 for Biological Applications

Abstract Advanced therapeutics require novel nanocarriers to ensure their functionality is preserved during transit. Zeolitic imidazolate frameworks (ZIFs) have emerged as promising materials in this field owing to their combined biocompatibility, high porosity, and tunable chemistry. While a diverse family of ZIFs has been reported, few have been explored beyond the prototypical ZIF‐8. Herein, the size‐controlled synthesis of three distinct ZIF‐76 analogs is demonstrated, overcoming the unique synthetic challenges intrinsic to the lta topology and complex crystallization kinetics associated with the mixed linker approach. This assesses the materials’ platform effectiveness for intracellular delivery first by exploring the structural and colloidal stability in biologically relevant media. To circumvent particle aggregation, fluorescently labeled DNA oligonucleotides are post‐synthetically attached to the ZIF surface. This modification significantly improves the colloidal stability in media and facilitates particle internalization tracking. Finally, the particle‐cell interactions are assessed, revealing rapid cell membrane association with macrophages, but not lung epithelial cells, and ZIF accumulation within macrophages which increased over time. Importantly, this study outlines a generalized approach toward expanding the available library of ZIFs for biological applications, enabling the potential for targeted therapeutic delivery for intracellular infections treatment.

Deneff, Jacob I.↗

Subventricular Accumulation of Cu in the Aging Mouse Brain Does Not Associate with Anticipated Increases in Markers of Oxidative Stress

Natural aging is associated with mild memory loss and cognitive decline, and age is the greatest risk factor for neurodegenerative diseases, such as Alzheimer’s disease. There is substantial evidence that oxidative stress is a major contributor to both natural aging and neurodegenerative disease, and coincidently, levels of redox active metals such as Fe and Cu are known to be elevated later in life. Recently, a pronounced age-related increase in Cu content has been reported to occur in mice and rats around a vital regulatory brain region, the subventricular zone of lateral ventricles. In our study herein, we have characterized lateral ventricle Cu content in a unique murine model of accelerated aging, senescence accelerated mouse-prone 8 (SAMP8) mice. Our results confirm an age-related increase in ventricle Cu content, consistent with the studies by others in wild-type mice and rats. Specifically, we observed Cu content to increase over the time frame 1 to 5 months and 5 to 9 months, but interestingly, no significant increase occurred between 9 and 12 months (although brain Cu content at 12 months was significantly elevated relative to 1 and 5 month-old animals). Despite the magnitude of Cu increase observed within the cells that comprise the subventricular zone of lateral ventricles (average 3 mM Cu, with isolated subcellular concentrations of 17 mM), we did not detect spectroscopic markers of thiol oxidation, protein aggregation, or lipid oxidation. The lack of evidence for oxidative stress in ex vivo animal tissue is in contrast to in vitro studies demonstrating that thiol, protein, and lipid oxidation is pronounced at these Cu concentrations. We suggest that our findings most likely indicate that the Cu ions in this brain region are sequestered in an unreactive form, possibly extended chains of Cu-thiolate complexes, which do not readily redox cycle in the aqueous cytosol. In conclusion, these results also appear to partially challenge the long-held view that age-related increases in brain metal content drive oxidative stress as we did not observe a concomitant association between age-related Cu increase and markers of oxidative stress, nor did we observe a net increase in Cu content between mice aged 9 and 12 months.

X-ray fluorescence↗

Galactosylation of xyloglucan is essential for the stabilization of the actin cytoskeleton and endomembrane system through the proper assembly of cell walls

Abstract Xyloglucan, a major hemicellulose, interacts with cellulose and pectin to assemble primary cell walls in plants. Loss of the xyloglucan galactosyltransferase MURUS3 (MUR3) leads to the deficiency of galactosylated xyloglucan and perturbs plant growth. However, it is unclear whether defects in xyloglucan galactosylation influence the synthesis of other wall polysaccharides, cell wall integrity, cytoskeleton behaviour, and endomembrane homeostasis. Here, we found that in mur3-7 etiolated seedlings cellulose was reduced, CELLULOSE SYNTHASE (CESA) genes were down-regulated, the density and mobility of cellulose synthase complexes (CSCs) were decreased, and cellulose microfibrils become discontinuous. Pectin, rhamnogalacturonan II (RGII), and boron contents were reduced in mur3-7 plants, and B-RGII cross-linking was abnormal. Wall porosity and thickness were significantly increased in mur3-7 seedlings. Endomembrane aggregation was also apparent in the mur3-7 mutant. Furthermore, mutant seedlings and their actin filaments were more sensitive to Latrunculin A (LatA) treatment. However, all defects in mur3-7 mutants were substantially restored by exogenous boric acid application. Our study reveals the importance of MUR3-mediated xyloglucan galactosylation for cell wall structural assembly and homeostasis, which is required for the stabilization of the actin cytoskeleton and the endomembrane system.

59 BASIC BIOLOGICAL SCIENCES↗

Tailoring catalyst layer structures for anion exchange membrane fuel cells by controlling the size of ionomer aggreates in dispersion

The development of anion exchange membranes and ionomers plays a critical role in performance of anion exchange membrane fuel cells. However, the optimal design of catalyst layer structures still remains unexplored despite its significance. Herein, the rational design guide is presented for cathode and anode catalyst layers using m-TPN1 ionomer by controlling the size of ionomer aggregates in dispersion and comparing various catalyst layer structures. The size of m-TPN1 aggregates decreases, creating a more uniform ionomer distribution and a larger triple-phase-boundary. As ionomer distribution of the cathode catalyst layer becomes more uniform, the power density of membrane-electrode-assembly is enhanced. Also, the power density at fully humidified condition strongly correlates with the porosity of anode catalyst layer due to the limitation of hydrogen transport at anode by water flooding.

42 ENGINEERING↗

Y-Type Non-Fullerene Acceptors with Outer Branched Side Chains and Inner Cyclohexane Side Chains for 19.36% Efficiency Polymer Solar Cells

Raising the lowest unoccupied molecular orbital (LUMO) energy level of Y-type non-fullerene acceptors can increase the open-circuit voltage (V oc ) and thus the photovoltaic performance of the current top performing polymer solar cells (PSCs). One of the viable routes is demonstrated by the successful Y6 derivative of L8-BO with the branched alkyl chains at the outer side. This will introduce steric hindrance and reduce intermolecular aggregation, thus open up the bandgap and raise the LUMO energy level. To take further advantages of the steric hindrance influence on optoelectronic properties of Y6 derivatives, two Y-type non-fullerene acceptors of BTP-Cy-4F and BTP-Cy-4Cl are designed and synthesized by adopting outer branched side chains and inner cyclohexane side chains. An outstanding V oc of 0.937 V is achieved in the D18:BTP-Cy-4F binary blend devices along with a power conversion efficiency (PCE) of 18.52%. With the addition of BTP-eC9 to extend the absorption spectral coverage, a remarkable PCE of 19.36% is realized finally in the related ternary blend devices, which is one of the highest values for single-junction PSCs at present. The results illustrate the great potential of cyclohexane side chains in constructing high-performance non-fullerene acceptors and their PSCs.

36 MATERIALS SCIENCE↗

Drastically different restructuring of airborne and surface-anchored soot aggregates

Combustion soot particles are fractal aggregates of hydrophobic spherules. Mixing of soot particles with other chemicals during atmospheric processing may partially offset their hydrophobicity, promoting water uptake and structural compaction. Here, we investigated morphological changes in fractal soot particles coated by sulfuric acid and then humidified, both in airborne and surface-bound states. Airborne soot was probed by tandem differential mobility analysis. Surface-bound soot was studied in a controlled microenvironment of a closed cell, using environmental transmission electron microscopy. After humidification, the airborne particles became fully compact, but the deposited particles showed only minor morphological changes despite significant water uptake. Although minor, those changes were detected during both water condensation and evaporation, indicating that condensation-evaporation cycles play an important role in atmospheric soot compaction. Lesser restructuring of deposited aggregates was caused by surface anchoring and coating loss, making anchoring an indispensable tool for preserving morphology of aggregates against changing experimental environment.

54 ENVIRONMENTAL SCIENCES↗

Modulating Solvation Structure in Concentrated Aqueous Organic Redox Flow Battery Electrolyte for Solubility and Transport Enhancement via Polycomplex Ion

Aqueous organic redox flow batteries hold great promise as a technology for creating economical grid energy storage using sustainable materials. Nonetheless, the solubility limit presents a universal barrier for all redox-active organic molecules. In this paper, a new approach is proposed to surpass the solubility limit by manipulating the solvation structure with polycomplex ion additives (PIA). Using poly(3,4-ethylenedioxythiophene) polystyrenesulfonate colloids as one example, its role in dismantling the rigid supramolecular clusters within the highly concentrated 7,8-dihydroxyphenazine-2-sulfonic acid electrolyte is investigated. 1 H and 23 Na NMR spectra and molecular dynamics simulation studies demonstrate that the bipolar structure of the PIA effectively disrupts the aggregations of DHPS and Na + ion in the highly concentrated anolyte, thus rendering a more flexible solvation structure and less restrictive ion transport, leading to substantially improved battery performance of an AORFB cell. The anolyte with PIA achieved 1.6 M and 74.3 Ah L –1 anolyte energy capacity.

25 ENERGY STORAGE↗

Meanders as a scaling motif for understanding of floodplain soil microbiome and biogeochemical potential at the watershed scale

Abstract Background Biogeochemical exports from watersheds are modulated by the activity of microorganisms that function over micron scales. Here, we tested the hypothesis that meander-bound regions share a core microbiome and exhibit patterns of metabolic potential that broadly predict biogeochemical processes in floodplain soils along a river corridor. Results We intensively sampled the microbiomes of floodplain soils located in the upper, middle, and lower reaches of the East River, Colorado. Despite the very high microbial diversity and complexity of the soils, we reconstructed 248 quality draft genomes representative of subspecies. Approximately one third of these bacterial subspecies was detected across all three locations at similar abundance levels, and ~ 15% of species were detected in two consecutive years. Within the meander-bound floodplains, we did not detect systematic patterns of gene abundance based on sampling position relative to the river. However, across meanders, we identified a core floodplain microbiome that is enriched in capacities for aerobic respiration, aerobic CO oxidation, and thiosulfate oxidation with the formation of elemental sulfur. Given this, we conducted a transcriptomic analysis of the middle floodplain. In contrast to predictions made based on the prominence of gene inventories, the most highly transcribed genes were relatively rare amoCAB and nxrAB (for nitrification) genes, followed by genes involved in methanol and formate oxidation, and nitrogen and CO 2 fixation. Within all three meanders, low soil organic carbon correlated with high activity of genes involved in methanol, formate, sulfide, hydrogen, and ammonia oxidation, nitrite oxidoreduction, and nitrate and nitrite reduction. Overall, the results emphasize the importance of sulfur, one-carbon and nitrogen compound metabolism in soils of the riparian corridor. Conclusions The disparity between the scale of a microbial cell and the scale of a watershed currently limits the development of genomically informed predictive models describing watershed biogeochemical function. Meander-bound floodplains appear to serve as scaling motifs that predict aggregate capacities for biogeochemical transformations, providing a foundation for incorporating riparian soil microbiomes in watershed models. Widely represented genetic capacities did not predict in situ activity at one time point, but rather they define a reservoir of biogeochemical potential available as conditions change.

54 ENVIRONMENTAL SCIENCES↗

Clean Cities and Communities Partnership 2023 Activity Report

This is the 2023 report for the Clean Cities and Communities (CC&C) partnership. It tracks the metrics that have been reported by individual coalitions and aggregated to the national level. It looks at the various outreach activities, grant activities, and implementation of clean transportation technologies. Such technologies include natural gas vehicles, electric vehicles, propane vehicles, hydrogen fuel cell vehicles, biodiesel, ethanol, idle reduction technologies, fuel economy improvement technologies, vehicle-miles-traveled reduction technologies, and off-road technologies. The CC&C partnership had an energy use impact of over 1 billion gallons in 2023 and reduced emissions by nine million tons. Outreach, engagement, and training activities increased 18% from last year.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗