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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 1,585 records · Page 88
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Fracture Intensity Impacts on Reaction Front Propagation and Mineral Weathering in Three‐Dimensional Fractured Media

Abstract Studying reaction front propagation in heterogeneous natural settings is challenging, but numerical simulations can provide insight into the varying spatial and temporal scales of reaction front propagation. Here, the impact of increasing fracture intensity on mineral dissolution rates, and the extent of reaction front propagation is investigated using reactive transport simulations in upscaled discrete fracture network domains with varied fracture intensity. Domain‐averaged dissolution rates vary less than 0.5 log units regardless of the fracture intensity, but the spatial distribution of reactions is controlled by the location and number of dead‐end fractures and the number of connected flowpaths through the domain. Higher fracture intensities lead to more weathering in the domain because of more available mineral for water‐rock interactions. We find that reaction fronts propagate through the primary flowpaths in the first 10,000 years of the simulation for a 10‐m length domain, then propagate into secondary flowpaths and dead‐end fractures between 10,000 and 100,000 years, and finally into the matrix over timescales of hundreds of thousands of years. The domain‐averaged reaction rates decrease through time corresponding to a transition from dissolution in advection‐dominated, fast‐flowing pathways, to dissolution in transport‐limited zones of disconnected fractures and matrix. Matrix dissolution, or dissolution under transport‐limited conditions, is the dominant process at late times in these simulations. The results of these simulations recreate the observed paradox found in nature where highly fractured hillslopes tend to be more weathered but have slower weathering rates, while hillslopes with fewer fractures, are less weathered but have higher dissolution rates.

58 GEOSCIENCES↗
DOE OSTI2013

Symmetry-Defying Iron Pyrite (FeS2) Nanocrystals through Oriented Attachment

Iron pyrite (fool’s gold, FeS2) is a promising earth abundant and environmentally benign semiconductor material that shows promise as a strong and broad absorber for photovoltaics and high energy density cathode material for batteries. However, controlling FeS2 nanocrystal formation (composition, size, shape, stoichiometry, etc.) and defect mitigation still remains a challenge. These problems represent significant limitations in the ability to control electrical, optical and electrochemical properties to exploit pyrite’s full potential for sustainable energy applications. Here, we report a symmetry-defying oriented attachment FeS2 nanocrystal growth by examining the nanostructure evolution and recrystallization to uncover how the shape, size and defects of FeS2 nanocrystals changes during growth. It is demonstrated that a well-controlled reaction temperature and annealing time results in polycrystal-to-monocrystal formation and defect annihilation, which correlates with the performance of photoresponse devices. This knowledge opens up a new tactic to address pyrite’s known defect problems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Electronic spectrum and characterization of diabatic potential energy surfaces for thiophenol

The electronic spectrum of thiophenol was simulated by a normal-mode sampling approach combined with TDDFT in the Tamm–Dancoff approximation (TDA). The vertical excitation energies were compared with electronic structure calculations by completely renormalized equation-of-motion coupled cluster theory with single and double excitations and noniterative inclusion of connected triples (CR-EOM-CCSD(T)) and by multi-reference perturbation theory. The spectrum was computed both with and without solvation effects, and these spectra are compared to each other and to experiment. Using multireference-perturbation-theory adiabatic wave functions and model-space diabatization by the fourfold way, diabatic potential energy surfaces of the lowest three singlet states ( 1 ππ, 1 ππ * , and 1 n π σ * ) were constructed along the S–H stretching coordinate, the C–C–S–H torsion coordinate, and the v 16a and v 16b normal coordinates. The first two of these two are primary coordinates for the photodissociation, and the diabatic crossing seams of the three states were calculated and plotted as functions of the two coordinates. The other two coordinates are out-of-plane ring distortion modes studied to assess the extent of their role in coupling the states near the first conical intersection, and the v 16a mode was shown to be an important coupling mode there. The current study is the first step toward a detailed mechanistic analysis of the photoinduced S–H fission process of thiophenol, a test system to understand 1 n π σ * -mediated reactions, at the same time already providing a better understanding of the thiophenol electronic excitations by clarifying the assignment of the experimental results.

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

Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport control

Wetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < pK a (P4VP) (pK a ~ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > pK a (P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitions in the BCP membrane. The potential-induced wetting/dewetting transition and the effect on cyclic voltammetry in the BCP@NEA structures is characterized as a function of the potential, pH and ionic strength. Additionally chronoamperometry and redox cycling experiments are used to further characterize the potential response. The multi-modal mass transport system proposed in this work will be useful for ultrasensitive sensing and single-molecule studies, which require long-time monitoring to explore reaction dynamics as well as molecular heterogeneity in nanoconfined volumes.

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

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction↗
DOE OSTI2014

Weakly nonlinear Rayleigh-Taylor instability of a finite-thickness fluid layer

A weakly nonlinear (WN) model has been developed for the Rayleigh-Taylor instability of a finite-thickness incompressible fluid layer (slab). We derive the coupling evolution equations for perturbations on the (upper) “linearly stable” and (lower) “linearly unstable” interfaces of the slab. Expressions of temporal evolutions of the amplitudes of the perturbation first three harmonics on the upper and lower interfaces are obtained. The classical feedthrough (interface coupling) solution obtained by Taylor [Proc. R. Soc. London A 201, 192 (1950)] is readily recovered by the first-order results. Our third-order model can depict the WN perturbation growth and the saturation of linear (exponential) growth of the perturbation fundamental mode on both interfaces. The dependence of the WN perturbation growth and the slab distortion on the normalized layer thickness (kd) is analytically investigated via the third-order solutions. Comparison is made with Jacobs-Catton's formula [J. W. Jacobs and I. Catton, J. Fluid Mech. 187, 329 (1988)] of the position of the “linearly unstable” interface. Using a reduced formula, the saturation amplitude of linear growth of the perturbation fundamental mode is studied. It is found that the finite-thickness effects play a dominant role in the WN evolution of the slab, especially when kd < 1. Thus, it should be included in applications where the interface coupling effects are important, such as inertial confinement fusion implosions and supernova explosions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Distortions in charged-particle images of laser direct-drive inertial confinement fusion implosions

Energetic charged particles generated by inertial confinement fusion (ICF) implosions encode information about the spatial morphology of the hotspot and dense fuel during the time of peak fusion reactions. The knock-on deuteron imager (KoDI) was developed at the Omega Laser Facility to image these particles in order to diagnose low-mode asymmetries in the hotspot and dense fuel layer of cryogenic deuterium–tritium ICF implosions. However, the images collected are distorted in several ways that prevent reconstruction of the deuteron source. In this paper, we describe these distortions and a series of attempts to mitigate or compensate for them. We present several potential mechanisms for the distortions, including a new model for scattering of charged particles in filamentary electric or magnetic fields surrounding the implosion. Particle-tracing is used to create synthetic KoDI data based on the filamentary field model that reproduces the main experimentally observed image distortions. We conclude that the filamentary scattering model best matches the observed image distortions. Finally, we discuss potential impacts of filamentary fields on other charged-particle diagnostics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Enabling accurate chemical modeling of shocked energetic materials using a machine learning interatomic potential

Understanding the complex chemistry of organic materials under dynamic compression is important for many applications, but it is challenging due to the large number of reactions occurring at various time scales. Here, in this study, we develop a machine learning potential based on Chebyshev polynomials to study the insensitive energetic material 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) under detonation. We discuss a strategy for constructing diverse training data needed to capture the complex chemistry of TATB. Our potential demonstrates strong transferability across a wide range of thermodynamic conditions and other explosives, enabling accurate and reliable chemical modeling of organic materials under extreme conditions. The efficiency of our approach allows for simulations over several nanoseconds and for large system sizes, providing detailed insights into the chemistry of shocked TATB. The model accurately reproduces experimental Hugoniot equation of state data, and our simulations reveal the rapid formation of nitrogen-rich carbon clusters following shock. The methods and datasets developed here offer a robust framework for accurate chemical modeling of other shocked organic energetic materials.

Chemistry↗
DOE OSTI2020

Observing 3-hydroxyanthranilate-3,4-dioxygenase in action through a crystalline lens

The synthesis of quinolinic acid from tryptophan is a critical step in the de novo biosynthesis of nicotinamide adenine dinucleotide (NAD + ) in mammals. Herein, the nonheme iron-based 3-hydroxyanthranilate-3,4-dioxygenase responsible for quinolinic acid production was studied by performing time-resolved in crystallo reactions monitored by UV-vis microspectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and X-ray crystallography. Seven catalytic intermediates were kinetically and structurally resolved in the crystalline state, and each accompanies protein conformational changes at the active site. Among them, a monooxygenated, seven-membered lactone intermediate as a monodentate ligand of the iron center at 1.59-Å resolution was captured, which presumably corresponds to a substrate-based radical species observed by EPR using a slurry of small-sized single crystals. Other structural snapshots determined at around 2.0-Å resolution include monodentate and subsequently bidentate coordinated substrate, superoxo, alkylperoxo, and two metal-bound enol tautomers of the unstable dioxygenase product. These results reveal a detailed stepwise O-atom transfer dioxygenase mechanism along with potential isomerization activity that fine-tunes product profiling and affects the production of quinolinic acid at a junction of the metabolic pathway.

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

A glimpse into the fungal metabolomic abyss: Novel network analysis reveals relationships between exogenous compounds and their outputs

Fungal specialized metabolites are a major source of beneficial compounds that are routinely isolated, characterized, and manufactured as pharmaceuticals, agrochemical agents, and industrial chemicals. The production of these metabolites is encoded by biosynthetic gene clusters that are often silent under standard growth conditions. There are limited resources for characterizing the direct link between abiotic stimuli and metabolite production. Herein, we introduce a network analysis-based, data-driven algorithm comprising two routes to characterize the production of specialized fungal metabolites triggered by different exogenous compounds: the direct route and the auxiliary route. Both routes elucidate the influence of treatments on the production of specialized metabolites from experimental data. The direct route determines known and putative metabolites induced by treatments and provides additional insight over traditional comparison methods. The auxiliary route is specific for discovering unknown analytes, and further identification can be curated through online bioinformatic resources. We validated our algorithm by applying chitooligosaccharides and lipids at two different temperatures to the fungal pathogen Aspergillus fumigatus. After liquid chromatography–mass spectrometry quantification of significantly produced analytes, we used network centrality measures to rank the treatments’ ability to elucidate these analytes and confirmed their identity through fragmentation patterns or in silico spiking with commercially available standards. Later, we examined the transcriptional regulation of these metabolites through real-time quantitative polymerase chain reaction. Our data-driven techniques can complement existing metabolomic network analysis by providing an approach to track the influence of any exogenous stimuli on metabolite production. Our experimental-based algorithm can overcome the bottlenecks in elucidating novel fungal compounds used in drug discovery.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Molecular Mechanism of Polysaccharide Acetylation by the Arabidopsis Xylan O-acetyltransferase XOAT1

Xylans are a major component of plant cell walls. O-Acetyl moieties are the dominant backbone substituents of glucuronoxylan in dicots and play a major role in the polymer-polymer interactions that are crucial for wall architecture and normal plant development. Here, we describe the biochemical, structural, and mechanistic characterization of Arabidopsis (Arabidopsis thaliana) xylan O-acetyltransferase 1 (XOAT1), a member of the plant-specific Trichome Birefringence Like (TBL) family. Detailed characterization of XOAT1-catalyzed reactions by real-time NMR confirms that it exclusively catalyzes the 2-O-acetylation of xylan, followed by nonenzymatic acetyl migration to the O-3 position, resulting in products that are monoacetylated at both O-2 and O-3 positions. In addition, we report the crystal structure of the catalytic domain of XOAT1, which adopts a unique conformation that bears some similarities to the a/ß/a topology of members of the GDSL-like lipase/acylhydrolase family. Finally, we use a combination of biochemical analyses, mutagenesis, and molecular simulations to show that XOAT1 catalyzes xylan acetylation through formation of an acyl-enzyme intermediate, Ac–Ser-216, by a double displacement bi-bi mechanism involving a Ser-His-Asp catalytic triad and unconventionally uses an Arg residue in the formation of an oxyanion hole.

acetylation↗
DOE OSTI2019

MAGE genes: Prognostic indicators in AL amyloidosis patients

Abstract A high frequency of MAGE‐CT (cancer testis) antigens are expressed in Multiple Myeloma (MM) patients; however, in other plasma cell dyscrasias, their potential function remains unclear. We measured the expression of MAGE‐CT genes (MAGE‐C1/CT7, MAGE‐A3, MAGE‐C2/CT10) in 105 newly diagnosed amyloid light‐chain (AL) amyloidosis patients between June 2013 and January 2018 at Peking University People's Hospital using real‐time quantitative polymerase chain reaction. In the newly diagnosed AL patients, the positive expression rates of patients with MAGE‐C1/CT7, MAGE‐C2/CT10 and MAGE‐A3 were 83.8% (88/105), 56.71% (38/67) and 22.0% (13/59) respectively. There was no significant correlation between organ propensity and MAGE‐CT gene expression. Changes in the MAGE‐C1/CT7 levels were consistent with a therapeutic effect. The expression levels of MAGE‐C1/CT7, MAGE‐C2/CT10 and MAGE‐A3 provide potentially effective clinical indicators for auxiliary diagnoses and monitoring treatment efficacy in AL amyloidosis patients.

Liu, Yang↗
DOE OSTI2018

Lens design challenges for scintillator-based neutron imaging

Neutron imaging is an important diagnostic to study inertial confinement fusion (ICF) implosions at the National Ignition Facility (NIF) using neutrons emitted in the fusion reactions. Analysis of time-gated images of the primary fusion (14.1 MeV) and down-scattered (6-12 MeV) neutrons based on their time-of-flight allows for the reconstruction of the burning hot spot undergoing fusion and the surrounding cold fuel. The Los Alamos National Laboratory (LANL) Advanced Imaging team has been providing these images since 2011. Currently, two additional lines of sight are being designed and built for NIF to allow three-dimensional reconstructions. Neutron imaging relies on the conversion of neutrons into light to be captured by an imaging system through the use of a scintillator. Although the current neutron imaging system utilizes a fiber scintillator array, a newly designed imaging system will consist of a thick monolithic scintillator and custom-designed lenses to collect the light. The custom lens has to resolve an image produced in the thick volume of the scintillator and therefore needs a large depth of field.

42 ENGINEERING↗
DOE OSTI2016

Improving the Accuracy of the Chebyshev Rational Approximation Method Using Substeps

The Chebyshev Rational Approximation Method (CRAM) for solving the decay and depletion of nuclides is shown to have a remarkable decrease in error when advancing the system with the same time step and microscopic reaction rates as the previous step. This property is exploited here to achieve high accuracy in any end-of-step solution by dividing a step into equidistant sub-steps. The computational cost of identical substeps can be reduced significantly below that of an equal number of regular steps, as the LU decompositions for the linear solves required in CRAM only need to be formed on the first substep. The improved accuracy provided by substeps is most relevant in decay calculations, where there have previously been concerns about the accuracy and generality of CRAM. Lastly, with substeps, CRAM can solve any decay or depletion problem with constant microscopic reaction rates to an extremely high accuracy for all nuclides with concentrations above an arbitrary limit.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2013

Isothermal DNA Assay to Detect Drug-Resistant Tuberculosis for Point-of-Care Diagnostics

Tuberculosis (TB) and multidrug-resistant tuberculosis (MDR-TB) remain a global health issue today. There exists an unmet need for a point-of-care TB diagnostic device that is accurate and suitable for use in resource-limited, high-burden settings. This study is the first demonstration of an isothermal DNA assay to identify MDR-TB, with future applications in a low-cost mobile phone diagnostic device. Using loop-mediated isothermal amplification, three primer signatures were identified to have high specificity, high sensitivity, and low limit of detection in amplifying M. tuberculosis (MTB) DNA. The use of a dsDNA-intercalating fluorescent dye enabled real-time visualization of the reactions and identification of positive amplifications. Moreover, the assay employs the addition of peptide nucleic acid (PNA) clamps to inhibit the amplification of drug-susceptible MTB DNA and allow the amplification of drug-resistant MTB DNA. Study results showed that combinations of two primer signatures and three PNA clamps inhibit the amplification of drug-susceptible MTB DNA. Results further showed that a relatively high concentration of PNA clamp relative to DNA template is required for inhibition. In future work, PNA clamp design will be improved to increase inhibition of drug-susceptible MTB DNA reactions. Additionally, the effects of the clamps on drug-resistant MTB DNA will be investigated; no amplification is expected.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Preliminary Simulation of the Corrosion Rate of Archaeological Glass

In this study, we make use of a micro-continuum modeling approach (the Kinetic-Microscopic-Continuum Model or KμC model) to capture the spatial distribution and identity of reaction products developing over time as a result of the archaeological glass corrosion, while also matching the time scales of alteration where possible. Since the glass blocks sat on the Mediterranean seafloor for 1800 years, the physical and chemical boundary conditions are largely constant. We focus on a fracture within the glass block identified by Verney-Carron et al. (2008) and simulate it as a 1D system, with a fixed concentration (Dirichlet) boundary corresponding to the interior of the fracture.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗