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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 1,117 records · Page 62
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Defining the Specificity of Carbohydrate–Protein Interactions by Quantifying Functional Group Contributions

Protein–carbohydrate interactions are significant in a wide range of biological processes, disruption of which has been implicated in many different diseases. The capability of glycan-binding proteins (GBPs) to specifically bind to the corresponding glycans allows GBPs to be utilized in glycan biomarker detection or conversely to serve as targets for therapeutic intervention. However, understanding the structural origins of GBP specificity has proven to be challenging due to their typically low binding affinities (mM) and their potential to display broad or complex specificities. Here we perform molecular dynamics (MD) simulations and post-MD energy analyses with the Poisson–Boltzmann and generalized Born solvent models (MM-PB/GBSA) of the Erythrina cristagalli lectin (ECL) with its known ligands, and with new cocrystal structures reported herein. While each MM-PB/GBSA parametrization resulted in different estimates of the desolvation free energy, general trends emerged that permit us to define GBP binding preferences in terms of ligand substructure specificity. Additionally, we have further decomposed the theoretical interaction energies into contributions made between chemically relevant functional groups. Based on these contributions, the functional groups in each ligand can be assembled into a pharmacophore comprised of groups that are either critical for binding, or enhance binding, or are noninteracting. It is revealed that the pharmacophore for ECL consists of the galactopyranose (Gal) ring atoms along with C6 and the O3 and O4 hydroxyl groups. This approach provides a convenient method for identifying and quantifying the glycan pharmacophore and provides a novel method for interpreting glycan specificity that is independent of residue-level glycan nomenclature. As a result, a pharmacophore approach to defining specificity is readily transferable to molecular design software and, therefore, may be particularly useful in designing therapeutics (glycomimetics) that target GBPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

Here, the entrance channel complex in the exothermic OH + CH 4 → H 2 O + CH 3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a -type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (j CH 4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same for all internal rotation states; however, subband origins are found to decrease with increasing j CH 4 . Measurements of deuterated complexes have also been made (OD–CH 4 , OH–CD 4 , and OD–CD 4 ), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH 4 and OD–CD 4 , for which the excited OX stretching state has a nearby CY 4 stretching fundamental (X, Y = H or D).

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

Genesis of Nanogalvanic Corrosion Revealed in Pearlitic Steel

Nanoscale, localized corrosion underpins billions of dollars in damage and material costs each year; however, the processes responsible have remained elusive due to the complexity of studying degradative material behavior at nanoscale liquid–solid interfaces. Recent improvements to liquid cell scanning/transmission electron microscopy and associated techniques enable this first look at the nanogalvanic corrosion processes underlying this widespread damage. Nanogalvanic corrosion is observed to initiate at the near-surface ferrite/cementite phase interfaces that typify carbon steel. In minutes, the corrosion front delves deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally, converting the ferrite to corrosion product normal to each buried cementite grain. Over the following few minutes, the corrosion product that lines each cementite grain undergoes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Hierarchical Epoxy Structures via Tunable Polymerization-Induced Phase Separation Combined with Additive Manufacturing

Polymerization-induced phase separation (PIPS) allows for the control of thermoset morphologies and properties, enabling the tuning of domain sizes and thermomechanical response. However, its use in generating substructural features in additively manufactured materials has been limited. In this work, we combine epoxy PIPS with UV curable acrylate and rheological modifiers to print nano- to macro-phase separating materials via a two-step, dual-cure approach. This method enables direct ink write printing of hierarchical structures with both controlled morphologies through phase separation and macroscale architecture through print design. We find that formulations for phase-separating materials require judicious incorporation of additives to enable printability and to provide sufficient green strength. Atomic force microscopy-nano infrared mapping reveals tunable, reticulated nano- to micron-scale domains of the resultant multiphase materials and their morphology changes due to additives, resulting in alterations to thermomechanical and tensile properties. Shape memory behavior is also demonstrated through multimaterial additive manufacturing of epoxies with functionally graded internal morphology using active mixing techniques, highlighting this method’s ability to fabricate complex architectures with controlled morphologies and thermomechanical response.

Van Meter, Kylie E [Organic Materials Science, San↗
DOE OSTI2013

Antiferromagnetic Spin Correlations Between Corner-Shared [FeO 5 ] 7- and [FeO 6 ] 9- Units, in the Novel Iron-Based Compound: BaYFeO 4

A novel quaternary compound in the Ba–Y–Fe-O phase diagram was synthesized by solid-state reaction and its crystal structure was characterized using powder X-ray diffraction. The crystal structure of BaYFeO 4 consists of a unique arrangement of Fe 3+ magnetic ions, which is based on alternate corner-shared units of [FeO 5 ] 7– square pyramids and [FeO 6 ] 9– octahedra. This results in the formation of stairwise channels of FeO polyhedra along the b crystallographic axis. The structure is described in an orthorhombic crystal system in the space group Pnma with lattice parameters a = 13.14455(1) Å, b = 5.694960(5) Å, and c = 10.247630(9) Å. The temperature-dependent magnetic susceptibility data reveal two antiferromagnetic (AFM) transitions at 33 and 48 K. An upturn in the magnetic susceptibility data above these transitions is observed, which does not reach its maximum even at 390 K. The field-dependent magnetization data at both 2 and 300 K show a nearly linear dependence and do not exhibit significant hysteresis. Heat capacity measurements between 2 and 200 K reveal only a broad anomaly without any indication of long-range ordering. The latter data set is not in good agreement with the magnetic susceptibility data, which makes it difficult to exactly determine the magnetic ground state of BaYFeO 4 . Accordingly, a temperature-dependent neutron diffraction study is in order, which will enable resolving this issue. The theoretical study of the relative strengths of magnetic exchange interactions along various possible pathways, using extended Hückel spin dimer analysis, shows that only interactions between square pyramidal and octahedral centers are significant, and among them, the intrachannel correlations are stronger than interchannel interactions. This is the first physical property study in such a magnetic ion substructure.

Wrobel, Friederike↗
DOE OSTI2020

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

RWD domain: a recurring module in kinetochore architecture shown by a Ctf19-Mcm21 complex structure

The proteins Ctf19, Okp1, Mcm21 and Ame1 are the components of COMA, a subassembly of budding-yeast kinetochores. We have determined the crystal structure of a conserved COMA subcomplex - the Ctf19 - Mcm21 heterodimer - from Kluyveromyces lactis. Both proteins contain 'double-RWD' domains, which together form a Y-shaped framework with flexible N-terminal extensions. The kinetochore proteins Csm1, Spc24 and Spc25 have related single RWD domains, and Ctf19 and Mcm21 associate with pseudo-twofold symmetry analogous to that in the Csm1 homodimer and the Spc24-Spc25 heterodimer. The double-RWD domain core of the Ctf19-Mcm21 heterodimer is sufficient for association with Okp1-Ame1; the less conserved N-terminal regions may interact with components of a more extensive 'CTF19 complex'. Our structure shows the RWD domain to be a recurring module of kinetochore architecture that may be present in other kinetochore substructures. Like many eukaryotic molecular machines, kinetochores may have evolved from simpler assemblies by multiplication of a few ancestral modules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Macromolecular X-ray structure determination using weak, single-wavelength anomalous data

We describe a likelihood-based method for determining the substructure of anomalously scattering atoms in macromolecular crystals that allows successful structure determination by single-wavelength anomalous diffraction (SAD) X-ray analysis with weak anomalous signal. With the use of partial models and electron density maps in searches for anomalously scattering atoms, testing of alternative values of parameters and parallelized automated model-building, this method has the potential to extend the applicability of the SAD method in challenging cases.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

A genome-wide association study of suicide attempts in the million veterans program identifies evidence of pan-ancestry and ancestry-specific risk loci

In this study, to identify pan-ancestry and ancestry-specific loci associated with attempting suicide among veterans, we conducted a genome-wide association study (GWAS) of suicide attempts within a large, multi-ancestry cohort of U.S. veterans enrolled in the Million Veterans Program (MVP). Cases were defined as veterans with a documented history of suicide attempts in the electronic health record (EHR; N = 14,089) and controls were defined as veterans with no documented history of suicidal thoughts or behaviors in the EHR ( N = 395,064). GWAS was performed separately in each ancestry group, controlling for sex, age and genetic substructure. Pan-ancestry risk loci were identified through meta-analysis and included two genome-wide significant loci on chromosomes 20 ( p = 3.64 × 10 -9 ) and 1 ( p = 3.69 × 10 -8 ). A strong pan-ancestry signal at the Dopamine Receptor D2 locus ( p = 1.77 × 10 -7 ) was also identified and subsequently replicated in a large, independent international civilian cohort ( p = 7.97 × 10 -4 ). Additionally, ancestry-specific genome-wide significant loci were also detected in African-Americans, European-Americans, Asian-Americans, and Hispanic-Americans. Pathway analyses suggested over-representation of many biological pathways with high clinical significance, including oxytocin signaling, glutamatergic synapse, cortisol synthesis and secretion, dopaminergic synapse, and circadian rhythm. These findings confirm that the genetic architecture underlying suicide attempt risk is complex and includes both pan-ancestry and ancestry-specific risk loci. Moreover, pathway analyses suggested many commonly impacted biological pathways that could inform development of improved therapeutics for suicide prevention.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

A yeast platform for high-level synthesis of tetrahydroisoquinoline alkaloids

The tetrahydroisoquinoline (THIQ) moiety is a privileged substructure of many bioactive natural products and semi-synthetic analogs. Plants manufacture more than 3,000 THIQ alkaloids, including the opioids morphine and codeine. While microbial species have been engineered to synthesize a few compounds from the benzylisoquinoline alkaloid (BIA) family of THIQs, low product titers impede industrial viability and limit access to the full chemical space. Here we report a yeast THIQ platform by increasing production of the central BIA intermediate ( S )-reticuline to 4.6 g L –1 , a 57,000-fold improvement over our first-generation strain. We show that gains in BIA output coincide with the formation of several substituted THIQs derived from amino acid catabolism. We use these insights to repurpose the Ehrlich pathway and synthesize an array of THIQ structures. This work provides a blueprint for building diverse alkaloid scaffolds and enables the targeted overproduction of thousands of THIQ products, including natural and semi-synthetic opioids.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Fragment-based drug nanoaggregation reveals drivers of self-assembly

Drug nanoaggregates are particles that can deleteriously cause false positive results during drug screening efforts, but alternatively, they may be used to improve pharmacokinetics when developed for drug delivery purposes. The structural features of molecules that drive nanoaggregate formation remain elusive, however, and the prediction of intracellular aggregation and rational design of nanoaggregate-based carriers are still challenging. We investigate nanoaggregate self-assembly mechanisms using small molecule fragments to identify the critical molecular forces that contribute to self-assembly. We find that aromatic groups and hydrogen bond acceptors/donors are essential for nanoaggregate formation, suggesting that both π-π stacking and hydrogen bonding are drivers of nanoaggregation. We apply structure-assembly-relationship analysis to the drug sorafenib and discover that nanoaggregate formation can be predicted entirely using drug fragment substructures. We also find that drug nanoaggregates are stabilized in an amorphous core-shell structure. These findings demonstrate that rational design can address intracellular aggregation and pharmacologic/delivery challenges in conventional and fragment-based drug development processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

The corrosion dealloying behavior of cold-worked (CW) Ni20Cr alloy (wt%) was studied in molten LiF-NaF-KF (or FLiNaK) salts at 600 °C, equal to a homologous temperature (TH) of 0.52. Alloys were cold-rolled to achieve reductions of thickness of 10%, 30%, and 50% introducing plastic deformation and a high density of dislocations. Potentiostatic holds (Eapplied) were applied in two different electrode potential regimes. At 1.75VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, Cr dealloying to Cr(II) and Cr(III) is predominant, while at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, both Ni and Cr are oxidized in molten FLiNaK at 600 °C. In these potential regimes, dealloyed Ni20Cr displayed bicontinuous porosity within the grain interior and at grain boundaries, driven by the high driving force for Cr dissolution and sustained by defect mediated outward solid state diffusion of Cr in parallel with surface diffusion of Ni. The bicontinuous porous structure developed was observed to undergo further coarsening and densification of the Ni-rich ligaments at a higher electrode potential. The main effect of CW observed is the introduction of plastic deformation and dislocation substructures that serve as short-circuit paths for Cr solid state diffusion to surfaces exposed to FLiNaK. This modified the evolution of the bicontinuous porous structure which increased with CW substantially. Kinetic analysis reveals that the Cr dealloying at +1.75 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ and 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ is initially charge transfer controlled, except for the 50% CW condition at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, where the process becomes limited by slow Cr defect mediated bulk diffusion. The rate determining factors are explored and compared to experimental results.

Chan, Ho Lun↗
DOE OSTI2020

Emergence of superconductivity in doped multiorbital Hubbard chains

Abstract We introduce a variational state for one-dimensional two-orbital Hubbard models that intuitively explains the recent computational discovery of pairing in these systems when hole doped. Our ansatz is an optimized linear superposition of Affleck–Kennedy–Lieb–Tasaki valence-bond states, rendering the combination a valence-bond liquid dubbed orbital resonant valence bond. We show that the undoped (one-electron/orbital) quantum state of two sites coupled into a global spin singlet is exactly written employing only spin-1/2 singlets linking orbitals at nearest-neighbor sites. Generalizing to longer chains defines our variational state visualized geometrically expressing our chain as a two-leg ladder, with one orbital per leg. As in Anderson’s resonating valence-bond state, our undoped variational state contains preformed singlet pairs that via doping become mobile, leading to superconductivity. Doped real materials with one-dimensional substructures, two near-degenerate orbitals, and intermediate Hubbard U / W strengths— W the carrier’s bandwidth—could realize spin-singlet pairing if on-site anisotropies are small. If these anisotropies are robust, spin-triplet pairing emerges.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Enantioselective α-functionalizations of ketones via allylic substitution of silyl enol ethers

The enantioselective construction of carbon-heteroatom and carbon-carbon bonds that are alpha to ketones leads to the formation of substructures that are ubiquitous in natural products, pharmaceuticals and agrochemicals. Traditional methods to form such bonds have relied on combining ketone enolates with electrophiles. Reactions with heteroatom-based electrophiles require special reagents in which the heteroatom, which is typically nucleophilic, has been rendered electrophilic by changes to the oxidation state. The resulting products usually require post-synthetic transformations to unveil the functional group in the final desired products. Moreover, different catalytic systems are typically required for the reaction of different electrophiles. In this work, we report a strategy for the formal enantioselective α-functionalization of ketones to form products containing a diverse array of substituents at the alpha position with a single catalyst. This strategy involves an unusual reversal of the role of the nucleophile and electrophile to form C-N, C-O, C-S and C-C bonds from a series of masked ketone electrophiles and a wide range of conventional heteroatom and carbon nucleophiles catalysed by a metallacyclic iridium catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Nitrene generation and transfer for unnatural biosynthesis in living cells

Abstract Synthetic biology has enabled the production of natural and unnatural products from inexpensive sustainable feedstocks. Yet, the scope of available products has been limited largely to compounds accessible from nature’s chemical reactions. Evolved enzymes can catalyse reactions of unnatural substrates or reactions not found in nature but often require the addition of synthetic reagents to purified enzymes or to resting cells containing those enzymes. Here we show that chemical reactions of metabolic intermediates produced intracellularly in living cells can include intermolecular nitrene transfers. The biosynthesis of N -acetoxyanilines, in combination with the generation and transfer of N -aryl nitrene intermediates from them catalysed by a cytochrome P450, generates amino alcohols, diamines, diarylamines and aminoalkyl arenes from simple carbon feedstocks. These products—common substructures of pharmaceuticals and agrochemicals—are challenging to synthesize by standard organic chemistry and were produced from inexpensive, renewable feedstocks. Evolution of the enzymes in this pathway showed that titres can be increased by engineering and that the products can be synthesized with high enantioselectivity.

Donnell, Isaac↗
DOE OSTI2025

Attosecond inner-shell lasing at ångström wavelengths

Since the invention of the laser, nonlinear effects such as filamentation, Rabi cycling and collective emission have been explored in the optical regime, leading to a wide range of scientific and industrial applications. X-ray free-electron lasers (XFELs) have extended many optical techniques to X-rays for their advantages of ångström-scale spatial resolution and elemental specificity. An example is XFEL-driven inner-shell Kα 1 (2p 3/2 → 1s 1/2 ) X-ray lasing in elements ranging from neon to copper, which has been used for nonlinear spectroscopy and development of new X-ray laser sources. Here, in this study, we show that strong lasing effects similar to those in the optical regime can occur at 1.5–2.1 Å wavelengths during high-intensity (>10 19 W cm −2 ) XFEL-driven Kα 1 lasing of copper and manganese. Depending on the temporal XFEL pump pulse substructure, the resulting X-ray pulses (about 10 6 −10 8 photons) can exhibit strong spatial inhomogeneities and spectral splitting, inhomogeneities and broadening. Three-dimensional Maxwell–Bloch calculations show that the observed spatial inhomogeneities result from X-ray filamentation and that the broad spectral features are driven by sub-femtosecond Rabi cycling. Our simulations indicate that these X-ray pulses can have pulse lengths of less than 100 attoseconds and coherence properties that provide opportunities for quantum X-ray optics applications.

47 OTHER INSTRUMENTATION↗
DOE OSTI2019

Irradiation-Dependent Helium Gas Bubble Superlattice in Tungsten

Abstract The implantation of noble gas atoms into metals at high gas concentrations can lead to the self-organization of nanobubbles into superlattices with symmetry similar to the metal host matrix. Here, we examine the influence of implantation parameters on the formation and structure of helium gas bubble superlattices within a tungsten host matrix to uncover mechanistic insight into the formation process. The determination of the size and symmetry of the gas bubbles was performed using a combination of small angle x-ray scattering and transmission electron microscopy. The former was demonstrated to be particularly useful in determining size and structure of the gas bubble superlattice as a function of irradiation conditions. Prior to the formation of a superlattice, we observe a persistent substructure characterized by inter-bubble spacings similar to those observable when the gas bubble superlattice has formed with very large ordering parameters. As the implantation fluence increases, the inter-bubble ordering parameter decreases, indicating improved ordering, until a superlattice is formed. Multiple implantation-specific differences were observed, including a temperature-dependent superlattice parameter that increases with increasing temperature and a flux-dependent superlattice parameter that decreases with increasing flux. The trends quantified here are in excellent agreement with our recent theoretical predictions for gas bubble superlattice formation and highlight that superlattice formation is strongly dependent on the diffusion of vacancy and implanted He atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Weak shock compaction on granular salt

This study conducted integrated experiments and computational modeling to investigate the speeds of a developing shock within granular salt and analyzed the effect of various impact velocities up to 245 m/s. Experiments were conducted on table salt utilizing a novel setup with a considerable bore length for the sample, enabling visualization of a moving shock wave. Experimental analysis using particle image velocimetry enabled the characterization of shock velocity and particle velocity histories. Mesoscale simulations further enabled advanced analysis of the shock wave’s substructure. In simulations, the shock front’s precursor was shown to have a heterogeneous nature, which is usually modeled as uniform in continuum analyses. The presence of force chains results in a spread out of the shock precursor over a greater ramp distance. With increasing impact velocity, the shock front thickness reduces, and the precursor of the shock front becomes less heterogeneous. Furthermore, mesoscale modeling suggests the formation of force chains behind the shock front, even under the conditions of weak shock. This study presents novel mesoscale simulation results on salt corroborated with data from experiments, thereby characterizing the compaction front speeds in the weak shock regime.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗