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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Comparative toxicity and efficacy of engineered anthrax lethal toxin variants with broad anti-tumor activities

We have previously designed and characterized versions of anthrax lethal toxin that are selectively cytotoxic in the tumor microenvironment and which display broad and potent anti-tumor activities in vivo. Here, we have performed the first direct comparison of the safety and efficacy of three engineered anthrax lethal toxin variants requiring activation by either matrix-metalloproteinases (MMPs), urokinase plasminogen activator (uPA) or co-localized MMP/uPA activities. C57BL/6J mice were challenged with six doses of engineered toxins via intraperitoneal (I.P.) or intravenous (I.V.) dose routes to determine the maximum tolerated dose for six administrations (MTD6) and dose-limiting toxicities. Efficacy was evaluated using the B16-BL6 syngraft model of melanoma; mice bearing established tumors were treated with six I.P. doses of toxin and tumor measurements and immunohistochemistry, paired with terminal blood work, were used to elaborate upon the anti-tumor mechanism and relative efficacy of each variant. We found that MMP-, uPA- and dual MMP/uPA-activated anthrax lethal toxins exhibited the same dose-limiting toxicity; dose-dependent GI toxicity. In terms of efficacy, all three toxins significantly reduced primary B16-BL6 tumor burden, ranging from 32% to 87% reduction, and they also delayed disease progression as evidenced by dose-dependent normalization of blood work values. While target organ toxicity and effective doses were similar amongst the variants, the dual MMP/uPA-activated anthrax lethal toxin exhibited the highest I.P. MTD6 and was 1.5–3-fold better tolerated than the single MMP- and uPA-activated toxins. Overall, we demonstrate that this dual MMP/uPA-activated anthrax lethal toxin can be administered safely and is highly effective in a preclinical model of melanoma. This modified bacterial cytotoxin is thus a promising candidate for further clinical development and evaluation for use in treating human cancers. - Highlights: • Toxicity and anti-tumor activity of protease-activated anthrax toxins were evaluated. • All anthrax toxin variants exhibited potent systemic anti-tumor activity in mice. • A dual MMP/uPA-activated anthrax toxin displayed a superior safety profile. • Clinical development of a dual MMP/uPA-activated anthrax toxin is feasible.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Cretaceous sequence stratigraphy of the northern Baltimore Canyon Trough: Implications for basin evolution and carbon storage

We evaluate the Cretaceous stratigraphy and carbon sequestration potential of the northern Baltimore Canyon Trough (NBCT) using >10,000 km of multi-channel seismic profiles integrated with geophysical logs, biostratigraphy, and lithology from 29 offshore wells. We identify and map six sequences resolved primarily at the stage level. Accommodation was dominated by thermal and non-thermal subsidence, though sequence boundaries correlate with regional and global sea-level changes, and the record is modified by igneous intrusion, active faulting, and changes in sediment supply and sources. Our stratigraphic maps illustrate a primary southern (central Appalachian) Early Cretaceous source that migrated northward during the Aptian and Albian. During the Cenomanian, sedimentation rates in the NBCT increased and depocenters shifted northward and landward. We show that deposition occurred in three phases: (1) earlier Cretaceous paleoenvironments were primarily terrestrial indicated by variable amplitude, chaotic seismic facies, serrated gamma logs, and heterolithic sandstones and mudstones with terrestrial microfossils; (2) the Albian to Cenomanian was dominated by deltaic paleoenvironments indicated by blocky, funnel-shaped, gamma-ray logs and clinoforms characterized by continuous high-amplitude seismic reflections with well-defined terminations; and (3) the Cenomanian and younger was marine shelf, inferred from mudstoneprone lithologies, peak gamma-ray values in well logs, and foraminiferal evidence. Long-term transgression and maximum water depths at the Cenomanian/Turonian boundary correlative with Ocean Anoxic Event 2 were followed by a regression and relative sea-level fall. We show that porous and permeable sandstones of three Aptian to Cenomanian highstand systems tracts are high-volume reservoirs for supercritical CO 2 storage that are confined by overlying deep water mudstones.

58 GEOSCIENCES↗
DOE OSTI2024

Enhanced nucleation mechanism in ruthenium atomic layer deposition: Exploring surface termination and precursor ligand effects with RuCpEt(CO)2

Miniaturization of microelectronic devices necessitates atomic precision in manufacturing techniques, particularly in the deposition of thin films. Atomic layer deposition (ALD) is recognized for its precision in controlling film thickness and composition on intricate three-dimensional structures. This study focuses on the ALD nucleation and growth mechanisms of ruthenium (Ru), a metal that has significant future implications for microelectronics. Despite its advantages, the deposition of a high surface-free energy material like Ru on a low surface-free energy material such as an oxide often faces challenges of large nucleation delays and non-uniform growth. To address these challenges, we explored the effectiveness of organometallic surface pretreatments using trimethylaluminum (TMA) or diethylzinc (DEZ) to enhance Ru film nucleation and growth. Our study employed a less-studied Ru precursor, cyclopentadienylethyl(dicarbonyl)ruthenium [RuCpEt(CO)2], which demonstrated promising results in terms of reduced nucleation delay and increased film continuity. Ru ALD was performed on silicon substrates with native oxide, using RuCpEt(CO)2 and O2 as coreactants. Our findings reveal that surface pretreatment significantly improves nucleation density and film thickness within the initial 60 ALD cycles, achieving up to a 3.2-fold increase in Ru surface coverage compared to nonpretreated substrates. Supported by density functional theory calculations, we propose that the enhanced nucleation observed with RuCpEt(CO)2 compared to previously-studied Ru(Cp)2 is due to two key mechanisms: the facilitated removal of CO ligands during deposition, which enhances the reactivity of the precursor, and a hydrogen-abstraction reaction involving the ethyl ligand of RuCpEt(CO)2 and the metal-alkyl groups on the surface. This study not only advances our understanding of Ru ALD processes but also highlights the significant impact of precursor chemistry and surface treatments in optimizing ALD for advanced microelectronic applications.

Materials Science↗
DOE OSTI2015

Structural analysis of the KRIT1 ankyrin repeat and FERM domains reveals a conformationally stable ARD-FERM interface

Cerebral cavernous malformations (CCM) are vascular dysplasias that usually occur in the brain and are associated with mutations in the KRIT1/CCM1, CCM2/MGC4607/OSM/Malcavernin, and PDCD10/CCM3/ TFAR15 genes. Here we report the 2.9 Å crystal structure of the ankyrin repeat domain (ARD) and FERM domain of the protein product of KRIT1 (KRIT1; Krev interaction trapped 1). The crystal structure reveals that the KRIT1 ARD contains 4 ankyrin repeats. There is also an unusual conformation in the ANK4 repeat that is stabilized by Trp-404, and the structure reveals a solvent exposed ankyrin groove. Domain orientations of the three copies within the asymmetric unit suggest a stable interaction between KRIT1 ARD and FERM domains, indicating a globular ARD–FERM module. It resembles the additional F0 domain found N-terminal to the FERM domain of talin. Structural analysis of KRIT1 ARD–FERM highlights surface regions of high evolutionary conservation, and suggests potential sites that could mediate interaction with binding partners. The structure therefore provides a better understanding of KRIT1 at the molecular level.

Ankyrin repeat↗
DOE OSTI2017

Proteomics-Based Tools for Evaluation of Cell-Free Protein Synthesis

Cell-free protein synthesis (CFPS) has the potential to produce enzymes, therapeutic agents, and other proteins, while circumventing difficulties associated with in vivo heterologous expression. However, the contents of the cell-free extracts used to carry out synthesis are generally not characterized, which hampers progress toward enhancing yield or functional activity of the target protein. Here we explored the utility of mass spectrometry (MS)-based proteomics for characterizing the bacterial extracts used for transcribing and translating gene sequences into proteins as well as the products of CFPS reactions. Full proteome experiments identified over 1000 proteins per reaction. The complete set of proteins necessary for transcription and translation were found, demonstrating the ability to define potential metabolic capabilities of the extract. Further, MS-based techniques allowed characterization of the CFPS product and provided insight into the synthesis reaction and potential functional activity of the product. These capabilities were demonstrated using two different CFPS products, the commonly used standard green fluorescent protein (GFP, 27 kDa) and the polyketide synthase DEBS1 (394 kDa). For the large, multidomain DEBS1, substantial premature termination of protein translation was observed. Additionally, MS/MS analysis, as part of a conventional full proteomics workflow, identified post-translational modifications, including the chromophore in GFP, as well as the three phosphopantetheinylation sites in DEBS1. A hypothesis-driven approach focused on these three sites identified that all were correctly modified for DEBS1 expressed in vivo but with less complete coverage for protein expressed in CFPS reactions. These post-translational modifications are essential for functional activity, and the ability to identify them with mass spectrometry is valuable for judging the success of the CFPS reaction. Collectively, the use of MS-based proteomics will prove advantageous for advancing the application of CFPS and related techniques.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Determining best practices for using genetic algorithms in molecular discovery

Genetic algorithms (GAs) are a powerful tool to search large chemical spaces for inverse molecular design. However, GAs have multiple hyperparameters that have not been thoroughly investigated for chemical space searches. In this tutorial, we examine the general effects of a number of hyperparameters, such as population size, elitism rate, selection method, mutation rate, and convergence criteria, on key GA performance metrics. Here, we show that using a self-termination method with a minimum Spearman’s rank correlation coefficient of 0.8 between generations maintained for 50 consecutive generations along with a population size of 32, a 50% elitism rate, three-way tournament selection, and a 40% mutation rate provides the best balance of finding the overall champion, maintaining good coverage of elite targets, and improving relative speedup for general use in molecular design GAs.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ruminococcus gnavus , a member of the human gut microbiome associated with Crohn’s disease, produces an inflammatory polysaccharide

A substantial and increasing number of human diseases are associated with changes in the gut microbiota, and discovering the molecules and mechanisms underlying these associations represents a major research goal. Multiple studies associate Ruminococcus gnavus , a prevalent gut microbe, with Crohn’s disease, a major type of inflammatory bowel disease. We have found that R. gnavus synthesizes and secretes a complex glucorhamnan polysaccharide with a rhamnose backbone and glucose sidechains. Chemical and spectroscopic studies indicated that the glucorhamnan was largely a repeating unit of five sugars with a linear backbone formed from three rhamnose units and a short sidechain composed of two glucose units. The rhamnose backbone is made from 1,2- and 1,3-linked rhamnose units, and the sidechain has a terminal glucose linked to a 1,6-glucose. This glucorhamnan potently induces inflammatory cytokine (TNFα) secretion by dendritic cells, and TNFα secretion is dependent on toll-like receptor 4 (TLR4). We also identify a putative biosynthetic gene cluster for this molecule, which has the four biosynthetic genes needed to convert glucose to rhamnose and the five glycosyl transferases needed to build the repeating pentasaccharide unit of the inflammatory glucorhamnan.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Crystal structures of the naturally fused CS and cytochrome b 5 reductase ( b 5 R) domains of Ncb5or reveal an expanded CS fold, extensive CS– b 5 R interactions and productive binding of the NAD(P) + nicotinamide ring

Ncb5or (NADH-cytochrome b 5 oxidoreductase), a cytosolic ferric reductase implicated in diabetes and neurological diseases, comprises three distinct domains, cytochrome b 5 ( b 5 ) and cytochrome b 5 reductase ( b 5 R) domains separated by a CHORD–Sgt1 (CS) domain, and a novel 50-residue N-terminal region. Understanding how interdomain interactions in Ncb5or facilitate the shuttling of electrons from NAD(P)H to heme, and how the process compares with the microsomal b 5 (Cyb5A) and b 5 R (Cyb5R3) system, is of interest. A high-resolution structure of the b 5 domain (PDB entry 3lf5) has previously been reported, which exhibits substantial differences in comparison to Cyb5A. The structural characterization of a construct comprising the naturally fused CS and b 5 R domains with bound FAD and NAD + (PDB entry 6mv1) or NADP + (PDB entry 6mv2) is now reported. The structures reveal that the linker between the CS and b 5 R cores is more ordered than predicted, with much of it extending the β-sandwich motif of the CS domain. This limits the flexibility between the two domains, which recognize one another via a short β-sheet motif and a network of conserved side-chain hydrogen bonds, salt bridges and cation–Π interactions. Notable differences in FAD–protein interactions in Ncb5or and Cyb5R3 provide insight into the selectivity for docking of their respective b 5 redox partners. The structures also afford a structural explanation for the unusual ability of Ncb5or to utilize both NADH and NADPH, and represent the first examples of native, fully oxidized b 5 R family members in which the nicotinamide ring of NAD(P) + resides in the active site. Finally, the structures, together with sequence alignments, show that the b 5 R domain is more closely related to single-domain Cyb5R proteins from plants, fungi and some protists than to Cyb5R3 from animals.

Benson, David R.↗
DOE OSTI2024

Plant‐produced SARS ‐ CoV ‐2 antibody engineered towards enhanced potency and in vivo efficacy

Summary Prevention of severe COVID‐19 disease by SARS‐CoV‐2 in high‐risk patients, such as immuno‐compromised individuals, can be achieved by administration of antibody prophylaxis, but producing antibodies can be costly. Plant expression platforms allow substantial lower production costs compared to traditional bio‐manufacturing platforms depending on mammalian cells in bioreactors. In this study, we describe the expression, production and purification of the originally human COVA2‐15 antibody in plants. Our plant‐produced mAbs demonstrated comparable neutralizing activity with COVA2‐15 produced in mammalian cells. Furthermore, they exhibited similar capacity to prevent SARS‐CoV‐2 infection in a hamster model. To further enhance these biosimilars, we performed three glyco‐ and protein engineering techniques. First, to increase antibody half‐life, we introduced YTE‐mutation in the Fc tail; second, optimization ofN‐linked glycosylation by the addition of a C‐terminal ER‐retention motif (HDEL), and finally; production of mAb in plant production lines lacking β‐1,2‐xylosyltransferase and α‐1,3‐fucosyltransferase activities (FX‐KO). These engineered biosimilars exhibited optimized glycosylation, enhanced phagocytosis and NK cell activation capacity compared to conventional plant‐produced S15 and M15 biosimilars, in some cases outperforming mammalian cell produced COVA2‐15. These engineered antibodies hold great potential for enhancingin vivoefficacy of mAb treatment against COVID‐19 and provide a platform for the development of antibodies against other emerging viruses in a cost‐effective manner.

Biotechnology & Applied Microbiology↗
DOE OSTI2011

Oak Ridge 25URC Tandem Accelerator 2008 SNEAP Lab Report

During FY 2008, the 25URC operated for slightly over 3,000 research hours. The radioactive species {sup 80}Ge and {sup 17,18}F accounted for 763 of these hours. This included an experiment using {sup 17}F which was only possible due to an improvement of a factor of 50 in beam intensity over our previous facility record. Twenty stable beam species were provided this year. Operation for the experimental program was at terminal potentials from 2.02 to 23.8 MV. Approximately 200 hours of conditioning were done to return the machine to operation after tank openings. There were six tank openings during the year: three scheduled for general maintenance and three unscheduled. Two of the unscheduled openings were required to correct shorting rod issues and the other was to reestablish communication with one of the major dead sections. On July 28, an event happened that caused all accelerators at the Holifield Radioactive Ion Beam Facility (HRIBF) to suspend operation. At approximately 8 AM on that Monday, during operations with approximately 12 {micro}A of 50-MeV protons on a uranium carbide target, delivering neutron-rich {sup 81}Zn beam to the new Low-energy Radioactive Ion Beam Spectroscopy Station (LeRIBSS), a radiological control technician (RCT) reported higher than normal radiation levels just outside the shield door to the IRIS1 vault (the room in which RIBs are produced at HRIBF). The measured dose rate equivalent was 4 mrem/hr. The presence of radiological contamination on the floor just outside the shield door was subsequently noted, as was the possible presence of airborne radioactivity. These observations were reported to facility management. Accelerators were put in standby immediately and the building evacuated. The event was subsequently declared a laboratory operational emergency. Parts of the building were cleared for reentry to collect belongings on Monday afternoon. The entire building was cleared for reoccupation on Tuesday morning after a detailed radiological survey found no contamination outside the shielded vaults. No decontamination was required. No individual received any detectable radiological dose as a result of this event. The 25URC tandem accelerator was given permission to resume operation with stable beams in early September, but radioactive ion production is still not allowed. Subsequent analysis indicated a release that consisted entirely of noble gasses (Xe and Kr isotopes). We believe we have identified two unrelated failures, one associated with the HVAC system and the other with the roughing system exhaust which accounts for both the escape of noble gasses into the IRIS1 vault and their migration outside the vault. An investigation team report is expected by October 24. At that time, corrective actions will be determined and the path to future radioactive ion beam production will be known. The break from operations allowed a few upgrades to be implemented. The most notable was the installation and commissioning of a SNICS ion source purchased from National Electrostatics Corporation (NEC). The SNICS replaced the old Alton/Aarhus source that we have used for many years. An ANU style gas cathode holder was purchased also but has not yet been implemented. The first beams have been produced by the source and the biggest problem encountered was reducing the beam for very low current experiments. A new power supply for the injection magnet was installed during this period also. Radioactive ion beam (RIB) development at the High Power Target Laboratory (HPTL) has been delayed this year while installing the platforms, conduits and equipment for the second Injector for Radioactive Ion Species (IRIS2) which is co-located with the HPTL facility. Therefore, the majority of development activities have been performed at the two off-line ion source test facilities (ISTF1 and ISTF2) and the On-Line Test Facility (OLTF). Both test facilities have been developing systems which will eventually be used with IRIS2. Two new tunable Ti:Sapphire lasers have been ordered for continuing development of an ion source based on laser ionization using all solid-state lasers. When these are delivered, we will have a complete laser system. The other ion source test facility is continuing development of a negative-ion cooler for beam purification using photodetachment. This process has been demonstrated to work well in three systems so far (removing Co from Ni, removing S from Cl, and removing O from F). The original ion cooler has been modified to allow for use on the IRIS2 platform. Testing of this modified device is starting now. The OLTF has been used to test new types of uranium carbide targets for the electron beam plasma source (which are used for neutron-rich RIB campaigns) and to test a novel ion source which may result in purified beams of radioactive strontium isotopes.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Interleaved multi-channel, multi-level, multi-quadrant DC-DC converters

Direct-current-to-direct-current (DC-DC) power converters that include two or more multi-quadrant, multi-level, DC-DC, switching converter subcircuits, connected in parallel at respective input and output sides, so as to provide a multi-channel, multi-quadrant, multi-level configuration, are disclosed. The DC-DC power converters further include a control circuit configured to control the switching converter subcircuits so that corresponding switching semiconductors in each of the switching converter subcircuits are switched in an interleaved manner. In some embodiments, each of the switching converter subcircuits is a three-level, neutral-point-clamped, four-quadrant DC-DC converter circuit. In other embodiments, each of the switching converter subcircuits is a three-level, neutral-point-clamped, two-quadrant DC-DC converter circuit. In any of these embodiments, a filter capacitor may be connected between across a pair of output terminals at the output sides of the switching converter subcircuits.

Du, Yu↗
DOE OSTI2014

Structural and functional characterization of human and murine C5a anaphylatoxins

The structure of the human C5aR antagonist, C5a-A8, reveals a three-helix bundle conformation similar to that observed for human C5a-desArg, whereas murine C5a and C5a-desArg both form the canonical four-helix bundle. These conformational differences are discussed in light of the differential C5aR activation properties observed for the human and murine complement anaphylatoxins across species. Complement is an ancient part of the innate immune system that plays a pivotal role in protection against invading pathogens and helps to clear apoptotic and necrotic cells. Upon complement activation, a cascade of proteolytic events generates the complement effectors, including the anaphylatoxins C3a and C5a. Signalling through their cognate G-protein coupled receptors, C3aR and C5aR, leads to a wide range of biological events promoting inflammation at the site of complement activation. The function of anaphylatoxins is regulated by circulating carboxypeptidases that remove their C-terminal arginine residue, yielding C3a-desArg and C5a-desArg. Whereas human C3a and C3a-desArg adopt a canonical four-helix bundle fold, the conformation of human C5a-desArg has recently been described as a three-helix bundle. Here, the crystal structures of an antagonist version of human C5a, A8{sup Δ71–73}, and of murine C5a and C5a-desArg are reported. Whereas A8{sup Δ71–73} adopts a three-helix bundle conformation similar to human C5a-desArg, the two murine proteins form a four-helix bundle. A cell-based functional assay reveals that murine C5a-desArg, in contrast to its human counterpart, exerts the same level of activition as murine C5a on its cognate receptor. The role of the different C5a conformations is discussed in relation to the differential activation of C5a receptors across species.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

COLLISIONLESS DAMPING AT ELECTRON SCALES IN SOLAR WIND TURBULENCE

The dissipation of turbulence in the weakly collisional solar wind plasma is governed by unknown kinetic mechanisms. Two candidates have been suggested to play an important role in the dissipation, collisionless damping via wave-particle interactions and dissipation in small-scale current sheets. High resolution spacecraft measurements of the turbulent magnetic energy spectrum provide important constraints on the dissipation mechanism. The limitations of popular fluid and hybrid numerical schemes for simulation of the dissipation of solar wind turbulence are discussed, and instead a three-dimensional kinetic approach is recommended. We present a three-dimensional nonlinear gyrokinetic simulation of solar wind turbulence at electron scales that quantitatively reproduces the exponential form of the turbulent magnetic energy spectrum measured in the solar wind. A weakened cascade model that accounts for nonlocal interactions and collisionless Landau damping also quantitatively agrees with the observed exponential form. These results establish that a turbulent cascade of kinetic Alfven waves that is terminated by collisionless Landau damping is sufficient to explain the observed magnetic energy spectrum in the dissipation range of solar wind turbulence.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Cryo-EM of the pathogenic VCP variant R155P reveals long-range conformational changes in the D2 ATPase ring

Single amino acid mutations in valosin containing protein (VCP/p97), a highly conserved member of the ATPases associated with diverse cellular activities (AAA) family of ATPases has been linked to a severe degenerative disease affecting brain, muscle and bone tissue. Previous studies have demonstrated the role of VCP mutations in altering the ATPase activity of the D2 ring; however the structural consequences of these mutations remain unclear. In this study, we report the three-dimensional (3D) map of the pathogenic VCP variant, R155P, as revealed by single-particle Cryo-Electron Microscopy (EM) analysis at 14 Å resolution. We show that the N-terminal R155P mutation induces a large structural reorganisation of the D2 ATPase ring. Results from docking studies using crystal structure data of available wild-type VCP in the EM density maps indicate that the major difference is localized at the interface between two protomers within the D2 ring. Consistent with a conformational change, the VCP R155P variant shifted the isoelectric point of the protein and reduced its interaction with its well-characterized cofactor, nuclear protein localization-4 (Npl4). Together, our results demonstrate that a single amino acid substitution in the N-terminal domain can relay long-range conformational changes to the distal D2 ATPase ring. Our results provide the first structural clues of how VCP mutations may influence the activity and function of the D2 ATPase ring. - Highlights: • p97{sub R155P} and p97{sub A232E} decrease the ability of p97 to bind to its co-factor Npl4. • p97{sub R155P} has a different isoelectric point than that of p97{sub R95G}, p97{sub A232E} and p97{sub WT}. • Mutation R155P changes principally the conformation of the D2 ring. • Mutation R155P modifies the interface between two protomers within the D2 ring.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

First-principles study of Al/Al 3 Ni interfaces

Al-Ni alloys have shown promise for high-temperature applications due to the strengthening of Al 3 Ni fibers resistant to coarsening and spheroidization up to 400°C. While the interface between Al and Al 3 Ni phases affects the coarsening rate of Al 3 Ni at elevated temperatures, its characteristics are largely unknown to date. Here, we have constructed various supercells to model this interface and performed a first-principles study based on density functional theory (DFT). We have considered three groups of Al/Al 3 Ni interfaces: experimentally reported orientation relationships from the solidification studies, crystallographically similar Fe-Fe 3 C pearlite interfaces, and the family of low-index (100) termination planes. We have analyzed the correlation between the DFT Al/Al 3 Ni interfacial energies and characteristic features, e.g., excess free volume and the number of broken bonds. We outline the further experimental and computational analysis required to improve the interface modeling of Al/Al 3 Ni.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Structures of Mycobacterium tuberculosis DosR and DosR-DNA Complex Involved in Gene Activation during Adaptation to Hypoxic Latency

On encountering low oxygen conditions, DosR activates the transcription of 47 genes, promoting long-term survival of Mycobacterium tuberculosis in a non-replicating state. Here, we report the crystal structures of the DosR C-terminal domain and its complex with a consensus DNA sequence of the hypoxia-induced gene promoter. The DosR C-terminal domain contains four {alpha}-helices and forms tetramers consisting of two dimers with non-intersecting dyads. In the DNA-bound structure, each DosR C-terminal domain in a dimer places its DNA-binding helix deep into the major groove, causing two bends in the DNA. DosR makes numerous protein-DNA base contacts using only three amino acid residues per subunit: Lys179, Lys182, and Asn183. The DosR tetramer is unique among response regulators with known structures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Influence of Alkyne Precursor Structure on Carbon Nanotube Chiral Distribution: Data-Dense Analysis Across Multiple Catalyst Types

Carbon nanotubes (CNTs) are a desirable material in the field of optoelectronics and semiconductors due to electronic properties (e.g., bandgap) that are dependent upon their chirality, defined by their diameter and lattice angle. Unfortunately, industrial-scale syntheses have yet to realize growth of a single desired chirality and instead rely on postsynthetic separation techniques to refine a chiral mixture, which increases process complexity and cost. Here, we studied the influence of precursor structure on chiral distribution, using a series of terminal alkyne precursors (acetylene, methylacetylene, vinylacetylene, 1-butyne, two enantiomers of 3-butyn-2-ol and a racemic mixture thereof) to grow CNTs across five transition-metal catalysts (Fe, FeMo, and three proportions of CoMo). Multiwavelength Raman spectroscopy on 5,145 spots (5 catalysts, 7 precursors, 3 lasers, and 49 distinct substrate locations on each) determined that acetylene grew the smallest diameter CNTs, while vinylacetylene produced fewer subnanometer CNTs. Though precursor structure did not dictate a uniform chiral shift, it was shown to broaden or narrow chiral distribution, while catalyst structure played a dominant role. In conclusion, this is consistent with metal-precursor binding occurring through unsaturated bonds in the hydrocarbons via the alkyne polymerization mechanism.

Carbon nanotubes↗
DOE OSTI2014

Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr) 3 O 4 (111) Mixed Oxide Surface

The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an α-Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

36 MATERIALS SCIENCE↗