Search NASA⌕ Search

SEARCH · Search NASA

Results for “broader”

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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

Abstract Coupled dinuclear copper oxygen cores (Cu 2 O 2 ) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O 2 transport and substrate oxidation in many organisms. μ ‐1,2‐ cis peroxido dicopper cores ( C P ) have been proposed as key structures in the early stages of O 2 binding in these proteins; their reversible isomerization to other Cu 2 O 2 cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic C P cores in biological and synthetic systems, the properties and reactivity of C P Cu 2 O 2 species remain largely unexplored. Herein, we report the reversible interconversion of μ ‐1,2‐ trans peroxido ( T P ) and C P dicopper cores. Ca II mediates this process by reversible binding at the Cu 2 O 2 core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O 2 activation in biomimetic systems.

Vargo, Natasha P.↗
DOE OSTI2023

Mechanisms of Biomolecular Self–Assembly Investigated Through In Situ Observations of Structures and Dynamics

Biomolecular self-assembly of hierarchical materials is a precise and adaptable bottom-up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning-based approaches, multiparametric characterization, and high-throughput methods can boost the development of biomolecular self-assembly. Furthermore, the objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self-assembly and to inspire the next generation of biomimetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A GPT‐4 Reticular Chemist for Guiding MOF Discovery**

Abstract We present a new framework integrating the AI model GPT‐4 into the iterative process of reticular chemistry experimentation, leveraging a cooperative workflow of interaction between AI and a human researcher. This GPT‐4 Reticular Chemist is an integrated system composed of three phases. Each of these utilizes GPT‐4 in various capacities, wherein GPT‐4 provides detailed instructions for chemical experimentation and the human provides feedback on the experimental outcomes, including both success and failures, for the in‐context learning of AI in the next iteration. This iterative human‐AI interaction enabled GPT‐4 to learn from the outcomes, much like an experienced chemist, by a prompt‐learning strategy. Importantly, the system is based on natural language for both development and operation, eliminating the need for coding skills, and thus, make it accessible to all chemists. Our collaboration with GPT‐4 Reticular Chemist guided the discovery of an isoreticular series of MOFs, with each synthesis fine‐tuned through iterative feedback and expert suggestions. This workflow presents a potential for broader applications in scientific research by harnessing the capability of large language models like GPT‐4 to enhance the feasibility and efficiency of research activities.

Chemistry↗
DOE OSTI2026

Direct Observation of Elusive (DTBM‐SEGPHOS)CuH Monomer Enables Mechanistic Insights Into Hydrocupration, Aggregation, and Dynamics of Alkene Functionalization Catalysis

The bulky diphosphine DTBM-SEGPHOS is widely employed in CuH-catalyzed transformations as it provides remarkably active catalyst systems. The transient (DTBM-SEGPHOS)CuH monomer (LCuH) is the often-invoked active species. However, its instability has prevented spectroscopic characterization and mechanistic elucidation, hindering mechanistic understanding. We report low-temperature NMR spectroscopic characterization of LCuH, enabling quantitative kinetic analysis of the stoichiometric hydrocupration and catalytic hydroboration of cyclopentene, as well as the structural identification of two CuH clusters. LCuH inserts cyclopentene at −43°C, reaffirming its high reactivity toward olefins. LCuH deactivates to form L 2 Cu 3 H 3 and L 2 Cu 4 H 4 clusters, in which LCuH dimerization initiates aggregation. Kinetic analysis of reactions of unactivated alkenes indicates that competing on-cycle alkene hydrocupration and LCuH dimerization impact performance, as catalyst deactivation and turnover occur on comparable timescales. Structure–activity analysis using atomistic simulations shows that the steric profile of DTBM-SEGPHOS increases the CuH dimerization barrier by ∼7.7 kcal mol−1 compared to that of SEGPHOS, rationalizing the unique ability of DTBM-SEGPHOS to stabilize a reactive monomer for hydrocupration of broader alkene substrates. These findings illustrate the fundamental design principle that steric control of aggregation governs CuH catalyst performance, explaining both the exceptional activity of (DTBM-SEGPHOS)CuH and the limitations imposed by competing deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Extrusion‐Based Printing of Nanostructured Fatty Acid Gels Incorporated in Hydrogels

Soft materials with unique nanostructures such as lamellar, hexagonal, and cubic morphologies can replicate complex structures that have potential in various fields, including biomedical and industrial applications. However, a key challenge in advancing the broader applications of 3D printing for these nanostructured soft materials is insufficient mechanical properties that hinder their printability and compromise structural stability in the final product. In this study, the suitability of a fatty acid‐based lamellar gel is evaluated for direct extrusion‐based 3D printing. Here, the lamellar gel with varying water content is integrated with a photocurable hydrogel to preserve the shape and stability of the final prints. Complex 2D and 3D design patterns are used to assess extrusion behavior, structural stability, and print precision under varying pressures. Small‐angle X‐ray Scattering (SAXS) measurements reveal the formation of lamellar nanostructures and confirm their retention after photocuring in various gels. Rheological analysis confirms that these gels exhibit key properties suitable for extrusion‐based 3D printing, such as shear‐thinning behavior. Additionally, tensile testing is conducted to evaluate the mechanical properties across cured print samples. This study underscores the potential of nanostructured gels as a robust and versatile platform, facilitating the development of materials engineered for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Magnetocaloric Effect in Lightly‐Doped Fe 5 Si 3 Single Crystals

Abstract Development of promising new materials for above room temperature magnetic cooling applications relies on careful balancing of structure and composition to maximize accessible metastable phases that can drive a strong magnetocaloric effect (MCE). However, the working temperatures of these materials may fall outside of desired application windows. In this work, it is shown that it is possible to control metastable phase stability temperatures of Fe 5 Si 3 through selection of appropriate spin and charge doping. Here, the parent material's desired structure appears only within a narrow temperature range from 1098 to 1303 K. Doping with Mn and P is shown to allow stabilization of the parent's high temperature phase and resulting MCE to room temperature. The structural and magnetic properties, and the magnetocaloric effect of single crystal Fe 4.83 Mn 0.16 Si 2.91 P 0.09 (FMSP) are investigated experimentally and theoretically. A first‐order magneto‐elastic transition is observed at 348 K, where magnetic onset is accompanied by a change in lattice volume without an apparent change in crystal symmetry. Although the trace Mn and P doping are found to decrease the T C , the maximum magnetic entropy change Δ S Max ( T ) and the relative cooling power (RCP) of FMSP are enhanced compared to polycrystalline Fe 5 Si 3 . As a result, an intrinsically broader entropy change over a larger temperature span is generated in the lightly doped single crystal of Fe 5 Si 3 . The magnetic moment of the system is also enhanced. Density functional theory (DFT) calculations are performed to gain microscopic insights into the experimental findings. The results suggest that the hexagonal Fe 5 Si 3 is a new giant room temperature MCE material that is on par with La–Fe–Si and Fe‐Mn‐P‐Si systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evaluation of a Geotechnical Compaction Model to Estimate Sediment Deformation

When surface ruts from vehicle activity occur above archeological deposits, there is a potential for an impact to the archeological record to occur. While impacts to the soil surface are relatively straightforward to describe, sub-surface disturbances are more difficult to quantify. In particular, disturbances to buried archeological materials can be difficult to characterize. Materials can be damaged by surface disturbances, but they can also be impacted even if they stay intact. Interpretation of intact materials relocated within the sediment column can be problematic. Traditional characterization methods (e.g. excavation) can also disturb archaeological materials. Here, we present a geotechnical compaction model that can be used to assist with sub-surface characterization under vehicle ruts formed during off-road travel. The model is based on a Boussinesq analysis of stress increase below a surface load. The change in bulk density resulting from compaction is assumed to be proportional to the stress increase. The model results were compared against pilot scale tests conducted with homogeneous sediment and field scale in-situ tests. The results indicate that the model generally agreed with measurements to within 20%, although only a single soil type was evaluated in these studies, with a narrow range of initial bulk densities and rut depths. While application of the model across a broader matrix of soil types, bulk densities and rut depths would increase confidence in the model, it appears that the model may be suitable for use in archeological field investigations. Potential uses include both compliance and research based field applications.

Fritz, Brad G.↗
DOE OSTI2023

Life-cycle analysis of sustainable aviation fuel production through catalytic hydrothermolysis

Catalytic hydrothermolysis (CH) is a sustainable aviation fuel (SAF) pathway that has been recently approved for use in aircraft fuel production. In alignment with broader sustainable aviation goals, SAF production through CH requires a quantitative assessment of carbon intensity (CI) impacts. In this study, a current-day life-cycle analysis (LCA) was performed on SAF produced via CH to determine the CI. Various oily feedstocks were considered, including vegetable oils (soybean, carinata, camelina and canola) and low-burden oils and greases (corn oil, yellow grease and brown grease). Life-cycle inventory data were collected on all processes within the CH LCA boundary: feedstock cultivation and/or collection, preprocessing, hydrothermal cleanup and CH, biocrude refining, fuel transportation and end use through combustion. Baseline results show that the CH-produced SAF can be generated with CI reductions ranging from 48 to 82% compared with conventional jet fuel. Modest improvements to CI can be achieved through incremental changes to the brown grease CH process, such as relaxing the dewatering specification and implementing renewable natural gas and electricity, which could decrease the CI from 22.9 to 7.9 g CO 2 e/MJ. Total CH fuel production potential was also assessed on the basis of current or near-future feedstock availability and CI. The total biofuel production potential of CH (SAF and renewable fuel co-products) in the US sums to approximately 3487 million gallons per year, with 97% of these volumes having a CI below 50% of that for petroleum jet fuel. The study shows that from an LCA perspective, CH offers a viable SAF pathway that is comparable with existing SAF pathways like hydroprocessed esters and fatty acids.

09 BIOMASS FUELS↗
DOE OSTI2023

Reductive amination cascades in cell‐free and resting whole cell formats for valorization of lignin deconstruction products

Abstract The selective introduction of amine groups within deconstruction products of lignin could provide an avenue for valorizing waste biomass while achieving a green synthesis of industrially relevant building blocks from sustainable sources. Here, we built and characterized enzyme cascades that create aldehydes and subsequently primary amines from diverse lignin‐derived carboxylic acids using a carboxylic acid reductase (CAR) and an ω‐transaminase (TA). Unlike previous studies that have paired CAR and TA enzymes, here we examine multiple homologs of each of these enzymes and a broader set of candidate substrates. In addition, we compare the performance of these systems in cell‐free and resting whole‐cell biocatalysis formats using the conversion of vanillate to vanillyl amine as model chemistry. We also demonstrate that resting whole cells can be recycled for multiple batch reactions. We used the knowledge gained from this study to produce several amines from carboxylic acid precursors using one‐pot biocatalytic reactions, several of which we report for the first time. These results expand our knowledge of these industrially relevant enzyme families to new substrates and contexts for environmentally friendly and potentially low‐cost synthesis of diverse aryl aldehydes and amines.

Biotechnology & Applied Microbiology↗
DOE OSTI2025

A GPU‐Accelerated Generative Adversarial Model for Causal Inference

We develop a GPU-accelerated machine learning generative adversarial model designed to facilitate causal inferences from observational data. Our model's theoretical framework is conceptualized in a manner that is amenable to being operable and scalable for high-performance computing platforms. We leverage GPU acceleration to develop a parallel evolutionary algorithm to achieve large-scale parallel computation of the model within a now widely accessible computing platform. This capability both enhances computational speedup and efficiency and also extends the use of the model to a broader range of substantive research domains while maintaining the underlying theoretical properties of the model.

GPU↗
DOE OSTI2024

h5bench: A unified benchmark suite for evaluating HDF5 I/O performance on pre‐exascale platforms

Summary Parallel I/O is a critical technique for moving data between compute and storage subsystems of supercomputers. With massive amounts of data produced or consumed by compute nodes, high‐performant parallel I/O is essential. I/O benchmarks play an important role in this process; however, there is a scarcity of I/O benchmarks representative of current workloads on HPC systems. Toward creating representative I/O kernels from real‐world applications, we have created h5bench , a set of I/O kernels that exercise hierarchical data format version 5 (HDF5) I/O on parallel file systems in numerous dimensions. Our focus on HDF5 is due to the parallel I/O library's heavy usage in various scientific applications running on supercomputing systems. The various tests benchmarked in the h5bench suite include I/O operations (read and write), data locality (arrays of basic data types and arrays of structures), array dimensionality (one‐dimensional arrays, two‐dimensional meshes, three‐dimensional cubes), I/O modes (synchronous and asynchronous). In this paper, we present the observed performance of h5bench executed along several of these dimensions on existing supercomputers (Cori and Summit) and pre‐exascale platforms (Perlmutter, Theta, and Polaris). h5bench measurements can be used to identify performance bottlenecks and their root causes and evaluate I/O optimizations. As the I/O patterns of h5bench are diverse and capture the I/O behaviors of various HPC applications, this study will be helpful to the broader supercomputing and I/O community.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Comparative Hydrophobic Core Dynamics Between Wild‐Type Amyloid‐β Fibrils, Glutamate‐3 Truncation, and Serine‐8 Phosphorylation

Abstract Post‐translational modifications (PTMs) of amyloid‐β (Aβ) species are implicated in the modulation of overall toxicities and aggregation propensities. We investigated the internal dynamics in the hydrophobic core of the truncated ΔE3 mutant fibrils of Aβ 1–40 and compared them with prior and new data for wild‐type fibrils as well as with phosphorylated S8 fibrils. Deuteron static solid‐state NMR techniques, spanning line‐shape analysis, longitudinal relaxation, and chemical exchange saturation transfer methods, were employed to assess the rotameric jumps of several methyl‐bearing and aromatic groups in the core of the fibrils. Taken together, the results indicate the rather significant influence of the PTMs on the hydrophobic core dynamics, which propagates far beyond the local site of the chemical modification. The phosphorylated S8 fibrils display an overall rigidifying of the core based on the higher activation barriers of motions than the wild‐type fibrils, whereas the ΔE3 fibrils induce a broader variety of changes, some of which are thermodynamic in nature rather than the kinetic ones.

Vugmeyster, Liliya↗
DOE OSTI2025

Influence of Photoemission Geometry on Timing and Efficiency in 4D Ultrafast Electron Microscopy

Broader adoption of 4D ultrafast electron microscopy (UEM) for the study of chemical, materials, and quantum systems is being driven by development of new instruments as well as continuous improvement and characterization of existing technologies. Perhaps owing to the still-high barrier to entry, the full range of capabilities of laser-driven 4D UEM instruments has yet to be established, particularly when operated at extremely low beam currents (~fA). Accordingly, with an eye on beam stability, we have conducted particle tracing simulations of unconventional off-axis photoemission geometries in a UEM equipped with a thermionic-emission gun. Specifically, we have explored the impact of experimentally adjustable parameters on the time-of-flight (TOF), the collection efficiency (CE), and the temporal width of ultrashort photoelectron packets. The adjustable parameters include the Wehnelt aperture diameter (DW), the cathode set-back position (Ztip), and the position of the femtosecond laser on the Wehnelt aperture surface relative to the optic axis (Rphoto). Notable findings include significant sensitivity of TOF to DW and Ztip, as well as non-intuitive responses of CE and temporal width to varying Rphoto. As a means to improve accessibility, practical implications and recommendations are emphasized wherever possible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Association Between Baseline Hepatic or Renal Function and Clinical Outcomes for Patients With Non–Small Cell Lung Cancer Treated With a PD –1/PD– L1 Blocking Antibody Using Real–World and Trial Data

Clinical trials have demonstrated the benefit of PD-1/PD-L1 blocking antibodies for the treatment of patients with advanced non-small cell lung cancer (NSCLC) in defined patient populations that often exclude patients with moderate or severe hepatic or renal impairment. We assessed the association between overall survival (OS) and baseline organ function in patients with advanced NSCLC treated with PD-1/PD-L1 blocking antibodies in real-world data (RWD; patient-level data from electronic health records) and pooled clinical trial data submitted to the US Food and Drug Administration (FDA). The Kaplan–Meier estimator was used to estimate OS in different subgroups based on organ function. Unadjusted and adjusted Cox proportional hazards models were used to estimate the association between OS and organ function. In this hypothesis-generating study, baseline renal impairment did not appear to be associated with OS, while patients with baseline liver impairment had shorter OS. RWD provided information on a broader range of renal and hepatic function than was evaluated in clinical trials and hold promise to complement trial data in better understanding populations not represented in clinical trials.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Carbon cycling across ecosystem succession in a north temperate forest: Controls and management implications

Despite decades of progress, much remains unknown about successional trajectories of carbon (C) cycling in north temperate forests. Drivers and mechanisms of these changes, including the role of different types of disturbances, are particularly elusive. To address this gap, we synthesized decades of data from experimental chronosequences and long-term monitoring at a well-studied, regionally representative field site in northern Michigan, USA. Our study provides a comprehensive assessment of changes in above- and belowground ecosystem components over two centuries of succession, links temporal dynamics in C pools and fluxes with underlying drivers, and offers several conceptual insights to the field of forest ecology. Our first advance shows how temporal dynamics in some ecosystem components are consistent across severe disturbances that reset succession and partial disturbances that slightly modify it: both of these disturbance types increase soil N availability, alter fungal community composition, and alter growth and competitive interactions between short-lived pioneer and longer-lived tree taxa. Further, these changes in turn affect soil C stocks, respiratory emissions, and other belowground processes. Second, we show that some other ecosystem components have effects on C cycling that are not consistent over the course of succession. For example, canopy structure does not influence C uptake early in succession but becomes important as stands develop, and the importance of individual structural properties changes over the course of two centuries of stand development. Third, we show that in recent decades, climate change is masking or overriding the influence of community composition on C uptake, while respiratory emissions are sensitive to both climatic and compositional change. In synthesis, we emphasize that time is not a driver of C cycling; it is a dimension within which ecosystem drivers such as canopy structure, tree and microbial community composition change. Changes in those drivers, not in forest age, are what control forest C trajectories, and those changes can happen quickly or slowly, through natural processes or deliberate intervention. Stemming from this view and a whole-ecosystem perspective on forest succession, we offer management applications from this work and assess its broader relevance to understanding long-term change in other north temperate forest ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Seasonal grassland productivity forecast for the U.S. Great Plains using Grass–Cast

Every spring, ranchers in the drought-prone U.S. Great Plains face the same difficult challenge —trying to estimate how much forage will be available for livestock to graze during the upcoming summer grazing season. To reduce this uncertainty in predicting forage availability, we developed an innovative new grassland productivity forecast system, named Grass-Cast, to provide science-informed estimates of growing season above ground net primary production (ANPP). Grass-Cast uses over 30 yr of historical data including weather and the satellite-derived normalized vegetation difference index (NDVI)—combined with ecosystem modeling and seasonal precipitation forecasts—to predict if rangelands in individual counties are likely to produce below-normal, near-normal, or above-normal amounts of grass biomass (lbs/ac). Grass-Cast also provides a view of rangeland productivity in the broader region, to assist in larger scale decision-making—such as where forage resources for grazing might be more plentiful if a rancher’s own region is at risk of drought. Grass-Cast is updated approximately every two weeks from April through July. Each Grass-Cast forecast provides three scenarios of ANPP for the upcoming growing season based on different precipitation outlooks. Near real-time 8-d NDVI can be used to supplement Grass-Cast in predicting cumulative growing season NDVI and ANPP starting in mid-April for the Southern Great Plains and mid-May to early June for the Central and Northern Great Plains. Here, we present the scientific basis and methods for Grass-Cast along with the county-level production forecasts from 2017 and 2018 for ten states in the U.S. Great Plains. The correlation between early growing season forecasts and the end-of growing season ANPP estimate is >50% by late May or early June. In a retrospective evaluation, we compared Grass-Cast end-of-growing season ANPP results to an independent dataset and found that the two agreed 69% of the time over a 20-yr period. Although some predictive tools exist for forecasting upcoming growing season conditions, none predict actual productivity for the entire Great Plains. The Grass-Cast system could be adapted to predict grassland ANPP outside of the Great Plains or to predict perennial biofuel grass production.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

A multidimensional stability framework enhances interpretation and comparison of carbon cycling response to disturbance

Abstract The concept of stability is central to the study and sustainability of vital ecosystem goods and services as disturbances increase globally. While ecosystem ecologists, including carbon (C) cycling scientists, have long‐considered multiple dimensions of disturbance response, our discipline lacks an agreed‐upon analytical framework for characterizing multidimensional stability. Here, we advocate for the broader adoption of a standardized and normalized multidimensional stability framework for analyzing disturbance response. This framework includes four dimensions of stability: the degree of initial change in C fluxes (i.e., resistance ); rate (i.e., resilience ) and variability (i.e., temporal stability ) of return to pre‐disturbance C fluxes; and the extent of return to pre‐disturbance C fluxes (i.e., recovery ). Using this framework, we highlight findings not readily seen from analysis of absolute fluxes, including trade‐offs between initial and long‐term C flux responses to disturbance; different overall stability profiles among fluxes; and, using a pilot dataset, similar relative stability of net primary production following fire and insect disturbances. We conclude that ecosystem ecologists’ embrace of a unifying multidimensional stability framework as a complement to approaches focused on absolute C fluxes could advance global change research by aiding in the novel interpretation, comprehensive synthesis, and improved forecasting of ecosystems’ response to an increasing array of disturbances.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Delayed fire mortality has long‐term ecological effects across the Southern Appalachian landscape

Abstract Fire is a critical ecological process to the forests of the Southern Appalachians. Where fire was excluded from forest types that historically burned frequently, unanticipated changes can occur when fire is reintroduced. For example, the development of new fuel characteristics can change the patterns of fire mortality and associated ecological responses. To test the fire effects of delayed fire mortality (mortality initiated by fire that occurs subsequent to the fire year) in the Southern Appalachians, USA, we developed a fire‐effects model using both field studies and remote sensing. We then simulated these effects at a landscape scale to estimate broader ecological effects. Fire‐effects models that accounted for delayed mortality increased landscape biomass removed annually (~23%) and increased the number of sites with high light conditions (leaf area index < 4) when compared to simulations that only account for immediate mortality. While delayed mortality occurred across species and age classes, it was especially prevalent among older trees (>100 years old) and fire‐resistant species ( Quercus spp.). Overall, regeneration (trees <20 years old) changed very little, even with the inclusion of delayed mortality. This evidence suggests that, even when accounting for delayed mortality, individual fires are unlikely to shift the landscape composition toward the conditions of forests prior to fire exclusion and may even increase mesophication long term due to the loss of overstory dominant xeric trees.

Robbins, Zachary J.↗