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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Harvest Initiated Volatile Organic Compound Emissions from In-Field Tall Wheatgrass

While crop and grassland usage continues to increase, the full diversity of plant-specific volatile organic compounds (VOCs) emitted from these ecosystems, including their implications for atmospheric chemistry and carbon cycling, remains poorly understood. It is particularly important to investigate VOCs in the context of potential biofuels: aside from the implications of largescale land use, harvest may shift both the flux and speciation of emitted VOCs. To this point, we evaluate the diversity of VOCs emitted both pre and postharvest from “Alkar” tall wheatgrass (Thinopyrum ponticum), a candidate biofuel that exhibits greater tolerance to frost and saline land compared to other grass varieties. Mature plants grown under field conditions (n = 6) were sampled for VOCs both pre- and postharvest (October 2022). Via hierarchical clustering of emitted VOCs from each plant, we observe distinct “volatilomes” (diversity of VOCs) specific to the pre- and postharvest conditions despite plant-to-plant variability. In total, 50 VOCs were found to be unique to the postharvest tall wheatgrass volatilome, and these unique VOCs constituted a significant portion (26%) of total postharvest signal. While green leaf volatiles (GLVs) dominate the speciation of postharvest emissions (e.g., 54% of unique postharvest VOC signal was due to 1-penten-3-ol), we demonstrate novel postharvest VOCs from tall wheatgrass that are under characterized in the context of carbon cycling and atmospheric chemistry (e.g., 3-octanone). Continuing evaluations will quantitatively investigate tall wheatgrass VOC fluxes, better informing the feasibility and environmental impact of tall wheatgrass as a biofuel.

09 BIOMASS FUELS↗
DOE OSTI2020

Recycling Epoxy by Vitrimerization: Influence of an Initial Thermoset Chemical Structure

Epoxy/anhydride cured thermosets are widely used in aerospace and wind energy structures. Recycling the enormous amounts of epoxy thermoset waste remains a global challenge. Vitrimerization, a practical, low-cost, eco-friendly and scalable method was developed for closed-loop recycling of the crosslinked epoxy by converting the permanent network into a vitrimer type dynamic network. Here we study the effect of virgin epoxy network properties on network reforming efficiency and the activation energy of the dynamic network by varying the epoxy/anhydride ratio. The results point out that the permanent network crosslink density and glass transition temperature have a more pronounced effect on vitrimerization efficiency by comparison with the concentration of free hydroxyl groups in the system. Furthermore, the result can be potentially used to better control vitrimerization efficiency in recycling epoxy thermoset polymers and tailor the vitrimerized products properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

In Silico Discovery of Multistep Chemistry Initiated by a Conical Intersection: The Challenging Case of Donor–Acceptor Stenhouse Adducts

Detailed mechanistic understanding of multistep chemical reactions triggered by internal conversion via a conical intersection is a challenging task that emphasizes limitations in theoretical and experimental techniques. We present a discovery-based, hypothesis-free computational approach based on first-principles molecular dynamics to discover and refine the switching mechanism of donor–acceptor Stenhouse adducts (DASAs). We simulate the photochemical experiment in silico, following the “hot” ground state dynamics for 10 ps after photoexcitation. Using state-of-the-art graphical processing units-enabled electronic structure calculations we performed in total ~2 ns of nonadiabatic ab initio molecular dynamics discovering (a) critical intermediates that are involved in the open-to-closed transformation, (b) several competing pathways which lower the overall switching yield, and (c) key elements for future design strategies. Finally, our dynamics describe the natural evolution of both the nuclear and electronic degrees of freedom that govern the interconversion between DASA ground-state intermediates, exposing significant elements for future design strategies of molecular switches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Global Atmosphere‐aerosol Model ICON‐A‐HAM2.3–Initial Model Evaluation and Effects of Radiation Balance Tuning on Aerosol Optical Thickness

Abstract The Hamburg Aerosol Module version 2.3 (HAM2.3) from the ECHAM6.3‐HAM2.3 global atmosphere‐aerosol model is coupled to the recently developed icosahedral nonhydrostatic ICON‐A (icon‐aes‐1.3.00) global atmosphere model to yield the new ICON‐A‐HAM2.3 atmosphere‐aerosol model. The ICON‐A and ECHAM6.3 host models use different dynamical cores, parameterizations of vertical mixing due to sub‐grid scale turbulence, and parameter settings for radiation balance tuning. Here, we study the role of the different host models for simulated aerosol optical thickness (AOT) and evaluate impacts of using HAM2.3 and the ECHAM6‐HAM2.3 two‐moment cloud microphysics scheme on several meteorological variables. Sensitivity runs show that a positive AOT bias over the subtropical oceans is remedied in ICON‐A‐HAM2.3 because of a different default setting of a parameter in the moist convection parameterization of the host models. The global mean AOT is biased low compared to MODIS satellite instrument retrievals in ICON‐A‐HAM2.3 and ECHAM6.3‐HAM2.3, but the bias is larger in ICON‐A‐HAM2.3 because negative AOT biases over the Amazon, the African rain forest, and the northern Indian Ocean are no longer compensated by high biases over the sub‐tropical oceans. ICON‐A‐HAM2.3 shows a moderate improvement with respect to AOT observations at AERONET sites. A multivariable bias score combining biases of several meteorological variables into a single number is larger in ICON‐A‐HAM2.3 compared to standard ICON‐A and standard ECHAM6.3. In the tropics, this multivariable bias is of similar magnitude in ICON‐A‐HAM2.3 and in ECHAM6.3‐HAM2.3. In the extra‐tropics, a smaller multivariable bias is found for ICON‐A‐HAM2.3 than for ECHAM6.3‐HAM2.3.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Corrosive Influence of Carbon Dioxide on Crack Initiation in Quartz: Comparison With Liquid Water and Vacuum Environments

The stimulation of crack growth in quartz and siliceous materials by injecting carbon dioxide (CO 2 ) represents a key technology in long-term carbon storage and in the development of natural gas wells. While this technology is widely used, the molecular impact of CO 2 interactions on the solid matrix is only incompletely understood. In this work, we employ reactive molecular dynamics simulations to study how the CO 2 fluid environment affects the mechanical properties of pre-cracked single-crystal quartz. The thermodynamic conditions of interest are those relevant to subsurface reservoirs. We report how structural properties of quartz—bond length distribution and crack tip shape—evolve upon introduction of a fluid. These properties are directly related to macroscopic quantities of the global stress-strain curves, thus reaffirming the inherent coupling across multiple scales for fluid-solid interactions in the subsurface. Here, we find that CO 2 reduces the fracture toughness of quartz by 12.1% compared to that of quartz in vacuum, thereby promoting crack growth and enhancing fluid transport in the subsurface.

58 GEOSCIENCES↗
DOE OSTI2022

The DOE E3SM Model Version 2: Overview of the Physical Model and Initial Model Evaluation

Abstract This work documents version two of the Department of Energy's Energy Exascale Earth System Model (E3SM). E3SMv2 is a significant evolution from its predecessor E3SMv1, resulting in a model that is nearly twice as fast and with a simulated climate that is improved in many metrics. We describe the physical climate model in its lower horizontal resolution configuration consisting of 110 km atmosphere, 165 km land, 0.5° river routing model, and an ocean and sea ice with mesh spacing varying between 60 km in the mid‐latitudes and 30 km at the equator and poles. The model performance is evaluated with Coupled Model Intercomparison Project Phase 6 Diagnosis, Evaluation, and Characterization of Klima simulations augmented with historical simulations as well as simulations to evaluate impacts of different forcing agents. The simulated climate has many realistic features of the climate system, with notable improvements in clouds and precipitation compared to E3SMv1. E3SMv1 suffered from an excessively high equilibrium climate sensitivity (ECS) of 5.3 K. In E3SMv2, ECS is reduced to 4.0 K which is now within the plausible range based on a recent World Climate Research Program assessment. However, a number of important biases remain including a weak Atlantic Meridional Overturning Circulation, deficiencies in the characteristics and spectral distribution of tropical atmospheric variability, and a significant underestimation of the observed warming in the second half of the historical period. An analysis of single‐forcing simulations indicates that correcting the historical temperature bias would require a substantial reduction in the magnitude of the aerosol‐related forcing.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c

Abstract The dynamics of photodissociation and recombination in heme proteins represent an archetypical photochemical reaction widely used to understand the interplay between chemical dynamics and reaction environment. We report a study of the photodissociation mechanism for the Fe(II)-S bond between the heme iron and methionine sulfur of ferrous cytochrome c . This bond dissociation is an essential step in the conversion of cytochrome c from an electron transfer protein to a peroxidase enzyme. We use ultrafast X-ray solution scattering to follow the dynamics of Fe(II)-S bond dissociation and 1 s 3 p (Kβ) X-ray emission spectroscopy to follow the dynamics of the iron charge and spin multiplicity during bond dissociation. From these measurements, we conclude that the formation of a triplet metal-centered excited state with anti-bonding Fe(II)-S interactions triggers the bond dissociation and precedes the formation of the metastable Fe high-spin quintet state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Sequence-specific dynamic DNA bending explains mitochondrial TFAM’s dual role in DNA packaging and transcription initiation

Abstract Mitochondrial transcription factor A (TFAM) employs DNA bending to package mitochondrial DNA (mtDNA) into nucleoids and recruit mitochondrial RNA polymerase (POLRMT) at specific promoter sites, light strand promoter (LSP) and heavy strand promoter (HSP). Herein, we characterize the conformational dynamics of TFAM on promoter and non-promoter sequences using single-molecule fluorescence resonance energy transfer (smFRET) and single-molecule protein-induced fluorescence enhancement (smPIFE) methods. The DNA-TFAM complexes dynamically transition between partially and fully bent DNA conformational states. The bending/unbending transition rates and bending stability are DNA sequence-dependent—LSP forms the most stable fully bent complex and the non-specific sequence the least, which correlates with the lifetimes and affinities of TFAM with these DNA sequences. By quantifying the dynamic nature of the DNA-TFAM complexes, our study provides insights into how TFAM acts as a multifunctional protein through the DNA bending states to achieve sequence specificity and fidelity in mitochondrial transcription while performing mtDNA packaging.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Chromatin binding by HORMAD proteins regulates meiotic recombination initiation

The meiotic chromosome axis coordinates chromosome organization and interhomolog recombination in meiotic prophase and is essential for fertility. In S. cerevisiae , the HORMAD protein Hop1 mediates the enrichment of axis proteins at nucleosome-rich islands through a central chromatin-binding region (CBR). Here, we use cryoelectron microscopy to show that the Hop1 CBR directly recognizes bent nucleosomal DNA through a composite interface in its PHD and winged helix–turn–helix domains. Targeted disruption of the Hop1 CBR-nucleosome interface causes a localized reduction of axis protein binding and meiotic DNA double-strand breaks (DSBs) in axis islands and leads to defects in chromosome synapsis. Synthetic effects with mutants of the Hop1 regulator Pch2 suggest that nucleosome binding delays a conformational switch in Hop1 from a DSB-promoting, Pch2-inaccessible state to a DSB-inactive, Pch2-accessible state to regulate the extent of meiotic DSB formation. Phylogenetic analyses of meiotic HORMADs reveal an ancient origin of the CBR, suggesting that the mechanisms we uncover are broadly conserved.

59 BASIC BIOLOGICAL SCIENCES↗