Search NASA⌕ Search

SEARCH · Search NASA

Results for “activities”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 595 records · Page 33

Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mg Pt , ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

25 ENERGY STORAGE↗

Active site remodeling in tumor-relevant IDH1 mutants drives distinct kinetic features and potential resistance mechanisms

Abstract Mutations in human isocitrate dehydrogenase 1 (IDH1) drive tumor formation in a variety of cancers by replacing its conventional activity with a neomorphic activity that generates an oncometabolite. Little is understood of the mechanistic differences among tumor-driving IDH1 mutants. We previously reported that the R132Q mutant unusually preserves conventional activity while catalyzing robust oncometabolite production, allowing an opportunity to compare these reaction mechanisms within a single active site. Here, we employ static and dynamic structural methods and observe that, compared to R132H, the R132Q active site adopts a conformation primed for catalysis with optimized substrate binding and hydride transfer to drive improved conventional and neomorphic activity over R132H. This active site remodeling reveals a possible mechanism of resistance to selective mutant IDH1 therapeutic inhibitors. This work enhances our understanding of fundamental IDH1 mechanisms while pinpointing regions for improving inhibitor selectivity.

60 APPLIED LIFE SCIENCES↗

Ligand efficacy shifts a nuclear receptor conformational ensemble between transcriptionally active and repressive states

Abstract Nuclear receptors (NRs) are thought to dynamically alternate between transcriptionally active and repressive conformations, which are stabilized upon ligand binding. Most NR ligand series exhibit limited bias, primarily consisting of transcriptionally active agonists or neutral antagonists, but not repressive inverse agonists—a limitation that restricts understanding of the functional NR conformational ensemble. Here, we report a NR ligand series for peroxisome proliferator-activated receptor gamma (PPARγ) that spans a pharmacological spectrum from repression (inverse agonism) to activation (agonism) where subtle structural modifications switch compound activity. While crystal structures provide snapshots of the fully repressive state, NMR spectroscopy and conformation-activity relationship analysis reveals that compounds within the series shift the PPARγ conformational ensemble between transcriptionally active and repressive conformations that are natively populated in the apo/ligand-free ensemble. Our findings reveal a molecular framework for minimal chemical modifications that enhance PPARγ inverse agonism and elucidate their influence on the dynamic PPARγ conformational ensemble.

Science & Technology - Other Topics↗

Range extender mediates long-distance enhancer activity

Although most mammalian transcriptional enhancers regulate their cognate promoters over distances of tens of kilobases, some enhancers act over distances in the megabase range1. The sequence features that enable such long-distance enhancer–promoter interactions remain unclear. Here we used in vivo enhancer-replacement experiments at the mouse Shh locus to show that short- and medium-range limb enhancers cannot initiate gene expression at long-distance range. We identify a cis-acting element, range extender (REX), that confers long-distance regulatory activity and is located next to a long-range limb enhancer of Sall1. The REX element has no endogenous enhancer activity. However, addition of the REX to other short- and mid-range limb enhancers substantially increases their genomic interaction range. In the most extreme example observed, addition of REX increased the range of an enhancer by an order of magnitude from its native 73 kb to 848 kb. The REX element contains highly conserved [C/T]AATTA homeodomain motifs that are critical for its activity. These motifs are enriched in long-range limb enhancers genome-wide, including the ZRS (zone of polarizing activity (ZPA) regulatory sequence), a benchmark long-range limb enhancer of Shh2. The ZRS enhancer with mutated [C/T]AATTA motifs maintains limb activity at short range, but loses its long-range activity, resulting in severe limb reduction in knock-in mice. In summary, we identify a sequence signature associated with long-range enhancer–promoter interactions and describe a prototypical REX element that is necessary and sufficient to confer long-distance activation by remote enhancers.

Bower, Grace↗

Dependency of active pressure and equation of state on stiffness of wall

Autonomous motion and motility are hallmarks of active matter. Active agents, such as biological cells and synthetic colloidal particles, consume internal energy or extract energy from the environment to generate self-propulsion and locomotion. These systems are persistently out of equilibrium due to continuous energy consumption. It is known that pressure is not always a state function for generic active matter. Torque interaction between active constituents and confinement renders the pressure of the system a boundary-dependent property. The mechanical pressure of anisotropic active particles depends on their microscopic interactions with a solid wall. Using self-propelled dumbbells confined by solid walls as a model system, we perform numerical simulations to explore how variations in the wall stiffness influence the mechanical pressure of dry active matter. In contrast to previous findings, we find that mechanical pressure can be independent of the interaction of anisotropic active particles with walls, even in the presence of intrinsic torque interaction. Particularly, the dependency of pressure on the wall stiffness vanishes when the stiffness is above a critical level. In such a limit, the dynamics of dumbbells near the walls are randomized due to the large torque experienced by the dumbbells, leading to the recovery of pressure as a state variable of density.

42 ENGINEERING↗

Long-term patterns of cave-exiting activity of hibernating bats in western North America

Understanding frequency and variation of cave-exiting activity after arousal from torpor of hibernating bats is important for bat ecology and conservation, especially considering white-nose syndrome. In winter from 2011 to 2018, we acoustically monitored, and counted in hibernacula, two species of conservation concern—western small-footed myotis ( Myotis ciliolabrum ) and Townsend’s big-eared bats ( Corynorhinus townsendii )—in 9 caves located in important habitat for these species in western North America. We investigated if cave-exiting activity differed by species, cave, number of hibernating bats, moon phase, and weather variables. Both species exited hibernacula during all winter months, but most activity occurred in March followed by November. Although we counted almost 15 times more Townsend’s big-eared bats during hibernacula surveys, we documented western small-footed myotis exiting caves 3 times more than Townsend’s big-eared bats. Cave-exiting activity increased with increasing number of hibernating bats, but more so for western small-footed myotis. Both species of bats were active during warm weather and low wind speeds. Western small-footed myotis were more active during colder temperatures, higher wind speeds, and greater change in barometric pressure than Townsend’s big-eared bats. Our results provide a long-term dataset of cave-exiting activity after arousal from torpor during hibernation for these species before the arrival of white-nose syndrome.

54 ENVIRONMENTAL SCIENCES↗

Transient pattern formation in an active matter contact poisoning model

Abstract One of the most notable features in repulsive particle based active matter systems is motility-induced-phase separation (MIPS) where a dense, often crystalline phase and low density fluid coexist. Most active matter studies involve time-dependent activity; however, there are many active systems where individual particles transition from living or moving to dead or nonmotile due to lack of fuel, infection, or poisoning. Here we consider an active matter particle system at densities where MIPS does not occur. When we add a small number of infected particles that can poison other particles, rendering them nonmotile, we find a rich variety of time dependent pattern formation, including MIPS, a wetting phase, and a fragmented state formed when mobile particles plow through a nonmotile packing. We map the patterns as a function of time scaled by epidemic duration, and show that the pattern formation is robust for a wide range of poisoning rates and activity levels. We also show that pattern formation does not occur in a random death model, but requires the promotion of nucleation by contact poisoning. Our results should be relevant to biological and active matter systems where there is some form of poisoning, death, or transition to nonmotility.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Persistence length regulates emergent dynamics in active roller ensembles

Active colloidal fluids, biological and synthetic, often demonstrate complex self-organization and the emergence of collective behavior. Spontaneous formation of multiple vortices has been recently observed in a variety of active matter systems, however, the generation and tunability of the active vortices not controlled by geometrical confinement remain challenging. Here, we exploit the persistence length of individual particles in ensembles of active rollers to tune the formation of vortices and to orchestrate their characteristic sizes. We use two systems and employ two different approaches exploiting shape anisotropy or polarization memory of individual units for control of the persistence length. We characterize the dynamics of emergent multi-vortex states and reveal a direct link between the behavior of the persistence length and properties of the emergent vortices. We further demonstrate common features between the two systems including anti-ferromagnetic ordering of the neighboring vortices and active turbulent behavior with a characteristic energy cascade in the particles velocity field energy spectra. Finally, our findings provide insights into the onset of spatiotemporal coherence in active roller systems and suggest a control knob for manipulation of dynamic self-assembly in active colloidal ensembles.

42 ENGINEERING↗

Highly efficient semi-hydrogenation in strained ultrathin PdCu shell and the atomic deciphering for the unlocking of activity-selectivity

Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core–shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd–Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core–shell nanocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of filamentation in activation and DNA sequence specificity of the sequence-specific endonuclease SgrAI

Filament formation by metabolic, biosynthetic, and other enzymes has recently come into focus as a mechanism to fine-tune enzyme activity in the cell. Filamentation is key to the function of SgrAI, a sequence-specific DNA endonuclease that has served as a model system to provide some of the deepest insights into the biophysical characteristics of filamentation and its functional consequences. Structure-function analyses reveal that, in the filamentous state, SgrAI stabilizes an activated enzyme conformation that leads to accelerated DNA cleavage activity and expanded DNA sequence specificity. The latter is thought to be mediated by sequence-specific DNA structure, protein–DNA interactions, and a disorder-to-order transition in the protein, which collectively affect the relative stabilities of the inactive, non-filamentous conformation and the active, filamentous conformation of SgrAI bound to DNA. Full global kinetic modeling of the DNA cleavage pathway reveals a slow, rate-limiting, second-order association rate constant for filament assembly, and simulations of in vivo activity predict that filamentation is superior to non-filamenting mechanisms in ensuring rapid activation and sequestration of SgrAI's DNA cleavage activity on phage DNA and away from the host chromosome. In vivo studies demonstrate the critical requirement for accelerated DNA cleavage by SgrAI in its biological role to safeguard the bacterial host. Collectively, these data have advanced our understanding of how filamentation can regulate enzyme structure and function, while the experimental strategies used for SgrAI can be applied to other enzymatic systems to identify novel functional roles for filamentation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regulation of NMDAR activation efficiency by environmental factors and subunit composition

NMDA receptors (NMDAR) convert the major excitatory neurotransmitter glutamate into a synaptic signal. A key question is how efficiently the ion channel opens in response to the rapid exposure to presynaptic glutamate release. Here, we applied glutamate to single channel outside-out patches and measured the successes of channel openings and the latency to first opening to assay the activation efficiency of NMDARs under different physiological conditions and with different human subunit compositions. For GluN1/GluN2A receptors, we find that various factors, including intracellular ATP and GTP, can enhance the efficiency of activation presumably via the intracellular C-terminal domain. Notably, an energy-based internal solution or increasing the time between applications to increase recovery time improved efficiency. However, even under these optimized conditions and with a 1-s glutamate application, there remained around 10–15% inefficiency. Channel activation became more inefficient with brief synaptic-like pulses of glutamate at 2 ms. Of the different NMDAR subunit compositions, GluN2B-containing NMDARs showed the lowest success rate and longest latency to first openings, highlighting that they display the most distinct activation mechanism. In contrast, putative triheteromeric GluN1/GluN2A/GluN2B receptors showed high activation efficiency. Despite the low open probability, NMDARs containing either GluN2C or GluN2D subunits displayed high activation efficiency, nearly comparable with that for GluN2A-containing receptors. These results highlight that activation efficiency in NMDARs can be regulated by environmental surroundings and varies across different subunits.

He, Miaomiao (ORCID:0000000203179136)↗

Logic operations with active topological defects

Logic operations performed by semiconductor-based transistors are the basis of modern computing. There is considerable interest in creating autonomous materials systems endowed with the capability to make decisions. In this work, we introduce the concept of using topological defects in active matter to perform logic operations. When an extensile active stress in a nematic liquid crystal is turned on, +1/2 defects can self-propel, in analogy to electron transport under a voltage gradient. By relying on hydrodynamic simulations of active nematics, we demonstrate that patterns of activity, when combined with surfaces imparting certain orientations, can be used to control the formation and transport of +1/2 defects. We further show that asymmetric high- and low-activity patterns can be used to create effective defect gates, tunnels, and amplifiers. The proposed active systems offer the potential to perform computations and transmit information in active soft materials, including actin-, tubulin-, and cell-based systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Review—Development of Highly Active and Stable Catalyst Supports and Platinum–Free Catalysts for PEM Fuel Cell

Metal-free, metal-containing, and template-assisted metal-containing nitrogen-modified carbon-based catalysts carbon composite supports, and highly active and electrochemically stable hybrid cathode catalysts for oxygen reduction reaction are reviewed in this manuscript. Here, novel procedures are developed for the synthesis of (i) highly catalytically active PGM-free catalyst and stable carbon composite catalyst supports. The carbon composite catalyst supports are engineered with optimized BET surface area and pore size distribution and with a well-defined kinetic and mass transfer region during the reaction and their performance is dicussed in detail in this review. The surface activation results in increasing carbon graphitization and inclusion of non-metallic active sites on the support surface. The USC catalysts exhibit the initial performance of 0.91 V and a maximum power density of 177 mW cm –2 , with well-defined kinetic and mass-transfer regions and ~2.5% H 2 O 2 production. Activated carbon composite support (ACCS) is modified to optimize its kinetic activity and its electrochemical stability shows excellent thermal stability and support stability under simulated start-up/shut-down operating conditions. The stabilities of various supports developed in this study are compared with those of a commercial Pt/C catalyst. The active sites for the ORR identified with electrochemical and physicochemical methods are pyridinic-N and quaternary-N.

25 ENERGY STORAGE↗

Impact of Proton Activity on Fuel-Cell Performance (CRADA Final Report)

The key attribute that is being investigated is the dependence of the oxygen-reduction and hydrogen-oxidation reaction kinetics on proton activity. The influence of proton activity on the kinetics is also important in the determination of limiting factors that impact overall fuel-cell performance. At lower humidities, which are required to simplify fuel-cell water and thermal management (especially for higher-temperature operation) and enable next generation fuel cells, the ionomer water content will be different than that in today’s fuel cells. Such changes in water content directly impact the activity and concentration of protons. Thus, it is necessary to quantify this impact of proton activity on the reaction kinetics, and to determine means to mitigate any detrimental impacts to enable high performance. To realize the above goals of understanding the intrinsic interactions of proton activity on hydrogen-oxidation and oxygen-reduction kinetics, systematic investigations were carried out and a novel technique, a rapid microelectrode with environmental control, was realized. The experimental campaign at LBNL worked alongside that of TokyoTech and both were complemented by mathematical modeling of the key phenomena. The results demonstrated a robust method to analyze the kinetic behavior and an impact of proton activity, although greater delineation in terms of ion concentration versus activity was not obtained fully due in part to limited lab access during the COVID pandemic.

30 DIRECT ENERGY CONVERSION↗

Developing an Active Learning algorithm for learning Bayesian classifiers under the Multiple Instance Learning scenario

In the Multiple Instance Learning scenario, the training data consists of instances grouped into bags, and each bag is labelled with whether it is positive, i.e. contains at least one positive instance. First, Active Learning, in which additional labels can be iteratively requested, has the potential to allow more accurate classifiers to be learned with less labels. Active Learning has been applied to the Multiple Instance Learning under two settings: when bag labels of unlabelled bags can be requested, and when instance labels within bags known to be positive can be requested. Second, Bayesian Active learning methods have the potential to learn accurate classifiers with few labels, because they explicitly track the classifier uncertainty and can thus address its knowledge gaps. Yet, there does not exist any Bayesian Active Learning method for the Multiple Instance Learning Scenario. In this work, we develop the first such method. We develop a Bayesian classifier for the Multiple Instance Learning scenario, show how it can be efficiently used for Bayesian Active Learning, and perform experiments assessing its performance. While its performance exceeds that when no Active Learning is used, it is sometimes better, sometimes worse than the naive baseline of uncertainty sampling, depending on the situation. This suggests future work: building more customizable Bayesian Active Learning methods for the Multiple Instance Scenario, customizable to whether bag or instance label accuracy is targeted, and the labeling budget.

97 MATHEMATICS AND COMPUTING↗

Baseline Hypothetical Facility for the Production of 131 I and 99 Mo using Activation Targets

This report describes a hypothetical facility for production of medical radioisotopes via activation under the Proliferation Resistance and Optimization (PRO-X) program. The facility uses neutron activation of non-special nuclear material (SNM) to produce the medical isotopes 131 I and 99 Mo at a throughput of 60 Ci/week of 131 I and 5 Ci/week of 99 Mo. The hypothetical design was carried out using a 10 MWt research reactor. The precursors used for the activation process were TeO2 for 131 I and MoO 3 for 99 Mo. The processes are performed in 3 hot cells used for target receipt, extraction, purification low specific activity (LSA) generator introduction, and packaging. A fourth hotcell is used for waste processing. The hot cell processing area takes up a footprint of 15.4 m 2 with the total footprint of the facility, including space for administrative offices, non-rad labs, quality assurance, and radiation buffer areas set at 763 m 2 . Waste is produced at a weekly rate of 257.8 g low activity solid waste and 8032.7 mL of low activity liquid waste, 8032 mL of which is water. This baseline hypothetical facility for production of medical isotopes via activation was then compared and contrasted to the hypothetical facility for production of medical isotopes via fission products to show the differences in approach for the two production modes. The two production modes had several highlighted differences including the overall facility and hot cell layout, the type and amount of waste produced by the respective facilities, and economic factors impacting production mode. Finally, a decision tree for which production mode might be more beneficial for an entrant into medical isotope production was developed based on the differences examined and the desired output of medical isotopes desired by the entrant.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Northern Hemisphere Extratropical Cyclone Activity in the Twentieth Century Reanalysis Version 3 (20CRv3) and Its Relationship with Continental Extreme Temperatures

In this study, we detect and track extratropical cyclones using 6-hourly mean sea level pressure data taken from the Twentieth Century Reanalysis version 3 (20CRv3) over the period 1951–2015 and compare them with those in the Interim and fifth generation of ECMWF reanalyses over the period 1979–2018. Three indices were employed to characterize cyclone activity, including cyclone count, cyclone intensity, and a cyclone activity index (CAI) that combines the count and intensity. The results show that the cyclone indices in the three datasets have comparable annual climatologies and seasonal evolution over the northern extratropical land and ocean in recent decades. Based on the cyclone indices over the period 1951–2010 in 80 ensemble members of 20CRv3, cyclone count and intensity are negatively correlated in winter and tend to be positively and weakly correlated in summer. The interannual CAI variability is dominated by the cyclone count variability. Regional mean cyclone activity can be well represented using the ensemble average cyclone index. We then examined the linkage of the cyclone activity in 20CRv3 and observed cold and warm extremes over Eurasia and North America over the period 1951–2010. In winter, the principal components of interannual cold and warm extreme anomalies are more correlated with the regional mean cyclone count index over Eurasia, while they are more correlated with the cyclone intensity index over North America. The temperature anomalies associated with the regional and ensemble mean cyclone count index explain about 10% (20%) of interannual cold (warm) extreme variances averaged over Eurasia. The temperature anomalies associated with the mean cyclone intensity explain about 10% of interannual cold and warm extreme variances over North America. Large-scale atmospheric circulation anomalies in association with cyclone activity and the induced temperature advection drive temperature anomalies over Eurasia and North America. In summer, circulation and thermal advection anomalies associated with cyclone activity are weak over the two continents. Hence, that season’s relationship between cyclone activity and extreme temperature variability is weak.

20CRv3↗

1,10-Phenanthroline-Iron Complex-Derived Fe-N-C Electrocatalysts: Enhanced Oxygen Reduction Activity and Stability Through Synthesis Tuning

The development of electrocatalysts composed of earth-abundant elements is essential for advancing the commercial application of Proton Exchange Membrane Fuel Cells (PEMFC). Among these, single-atom electrocatalysts, such as Fe-N-C, show great promise for the oxygen reduction reaction (ORR). This study aims to improve the ORR activity and stability of Fe-N-C electrocatalysts by fine-tuning the straightforward 1,10-phenanthroline-iron complexation synthesis method. Key parameters, including iron-to-phenanthroline ratio, carbon powder surface area, and pyrolysis temperature were systematically varied to evaluate their influence on the resulting electrocatalysts. The findings of this study revealed that the electrocatalysts synthesized with 1,10-phenanthroline (Phen) and high-surface-area Black Pearls (BP) possessed much better ORR activity than electrocatalysts prepared by using Vulcan carbon (lower surface area). Interestingly, electrocatalysts prepared with BP, but with a non-bidentate nitrogen-containing ligand molecule, such as imidazole, showed a much poorer activity, as the resulting material predominantly consisted of inactive structures, such as encapsulated iron nanoparticles and iron oxide, as evidenced by HR-TEM, EXAFS, and XRD. Therefore, the results suggest that only the synergistic combination of the bidentate ligand phenanthroline (Phen) and the high-surface-area carbon support (BP) favored the formation of ORR-active Fe-N-C single-atom species upon pyrolysis. The study also unveiled a significant enhancement in electrocatalyst stability during accelerated durability tests (and air storage) as the pyrolysis temperature was increased from 700 to 1300 °C, albeit at the expense of ORR activity, likely resulting from the generation of iron particles. Pyrolysis at 1050 °C yielded the electrocatalyst with the most favorable balance of activity and stability in rotating disk measurements, while maintaining moderate durability under PEM fuel cell operation. The insights obtained in this study may guide the development of more active efficient and durable electrocatalysts, synthesized via a simple method using earth-abundant elements, for application in PEMFC cathodes.

30 DIRECT ENERGY CONVERSION↗