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At least 415 records · Page 23

Melting and density of MgSiO 3 determined by shock compression of bridgmanite to 1254GPa

The essential data for interior and thermal evolution models of the Earth and super-Earths are the density and melting of mantle silicate under extreme conditions. Here, we report an unprecedently high melting temperature of MgSiO 3 at 500 GPa by direct shockwave loading of pre-synthesized dense MgSiO3 (bridgmanite) using the Z Pulsed Power Facility. We also present the first high-precision density data of crystalline MgSiO 3 to 422 GPa and 7200 K and of silicate melt to 1254 GPa. The experimental density measurements support our density functional theory based molecular dynamics calculations, providing benchmarks for theoretical calculations under extreme conditions. The excellent agreement between experiment and theory provides a reliable reference density profile for super-Earth mantles. Furthermore, the observed upper bound of melting temperature, 9430 K at 500 GPa, provides a critical constraint on the accretion energy required to melt the mantle and the prospect of driving a dynamo in massive rocky planets.

58 GEOSCIENCES↗

Detection of innate immune response modulating impurities (IIRMI) in therapeutic peptides and proteins: Impact of excipients

Unintended immunogenicity can affect the safety and efficacy of therapeutic proteins and peptides, so accurate assessments of immunogenicity risk can aid in the selection, development, and regulation of biologics. Product- and process- related impurities can act as adjuvants that activate the local or systemic innate immune response increasing the likelihood of product immunogenicity. Thus, assessing whether products have innate immune response modulating impurities (IIRMI) is a key component of immunogenicity risk assessments. Identifying trace levels of individual IIRMI can be difficult and testing individually for all potential impurities is not feasible. Therefore, to mitigate the risk, cell-based assays that use human blood cells or monocyte-macrophage reporter cell lines are being developed to detect minute quantities of impurities capable of eliciting innate immune activation. As these are cell-based assays, there is concern that excipients could blunt the cell responses, masking the presence of immunogenic IIRMI. Here, we explore the impact of frequently used excipients (non-ionic detergents, sugars, amino acids, bulking agents) on the sensitivity of reporter cell lines (THP-1- and RAW-Blue cells) and fresh human blood cells to detect purified TLR agonists as model IIRMI. We show that while excipients do not modulate the innate immune response elicited by TLR agonists in vivo, they can impact on the sensitivity of cell-based IIRMI assays. Reduced sensitivity to detect LPS, FSL-1, and other model IIRMI was also evident when testing 3 different recombinant drug products, product A (a representative mAb), B (a representative growth factor), C (a representative peptide), and their corresponding formulations. These results indicate that product formulations need to be considered when developing and validating cell-based assays for assessing clinically relevant levels of IIRMI in therapeutic proteins. Optimization of reporter cells, culture conditions and drug product concentration appear to be critical to minimize the impact of excipients and attain sensitive and reproducible assays.

60 APPLIED LIFE SCIENCES↗

Adaptive complex nanocomposite alloys for burning plasma-material interface tunability (Final Report)

The focus of this program is discovery and development of novel self-healing and adaptive materials for the PMI (plasma-material interface) envisioned for future plasma-burning extreme environments in thermonuclear fusion reactors that can provide enhanced radiation-tolerance or resistance. This program was conceived and stems from the PI’s DOE Early Career Award work on harnessing nanotechnology and mesoscale materials design in refractory metals to address gaps in PMI research. These gaps pertain to the lack of understanding of multi-scale interactions at the plasma-material interface and the development of novel material interfaces that can be designed to adapt to extreme fusion reactor conditions. The final report is separated into two primary sections: The first section consists of the program’s first two years (FY16-FY17) performance period. The second section consists of FY18 to FY19 period, where the FY19 period was a supplemental addition to support the completion of a PhD thesis and continuation of another. This work consists of an excellent team consisting of a co-PI, one postdoctoral researcher, two graduate students, two undergraduate students and collaborators both domestic and abroad.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Characterizing inhibitors of human AP endonuclease 1

AP endonuclease 1 (APE1) processes DNA lesions including apurinic/apyrimidinic sites and 3´-blocking groups, mediating base excision repair and single strand break repair. Much effort has focused on developing specific inhibitors of APE1, which could have important applications in basic research and potentially lead to clinical anticancer agents. We used structural, biophysical, and biochemical methods to characterize several reported inhibitors, including 7-nitroindole-2-carboxylic acid (CRT0044876), given its small size, reported potency, and widespread use for studying APE1. Intriguingly, NMR chemical shift perturbation (CSP) experiments show that CRT0044876 and three similar indole-2-carboxylic acids bind a pocket distal from the APE1 active site. A crystal structure confirms these findings and defines the pose for 5-nitroindole-2-carboxylic acid. However, dynamic light scattering experiments show the indole compounds form colloidal aggregates that could bind (sequester) APE1, causing nonspecific inhibition. Endonuclease assays show the compounds lack significant APE1 inhibition under conditions (detergent) that disrupt aggregation. Thus, binding of the indole-2-carboxylic acids at the remote pocket does not inhibit APE1 repair activity. Myricetin also forms aggregates and lacks APE1 inhibition under aggregate-disrupting conditions. Two other reported compounds (MLS000552981, MLS000419194) inhibit APE1 in vitro with low micromolar IC50 and do not appear to aggregate in this concentration range. However, NMR CSP experiments indicate the compounds do not bind specifically to apo- or Mg 2+ -bound APE1, pointing to a non-specific mode of inhibition, possibly DNA binding. Our results highlight methods for rigorous interrogation of putative APE1 inhibitors and should facilitate future efforts to discover compounds that specifically inhibit this important repair enzyme.

59 BASIC BIOLOGICAL SCIENCES↗

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of five-membered ring structures via reactions of o -benzyne

The formation of five-membered ring structures is important for the generation of curved and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) under combustion conditions. Here, we report the identification of the indenyl (C 9 H 7 ) radical – the simplest aromatic hydrocarbon radical carrying an adjacent five- and six-membered ring, as the major product of the o-benzyne (o-C 6 H 4 ) reaction with propargyl (C 3 H 3 ). Because real flames exhibit a complex chemistry, elucidation of a specific reaction is very challenging. Instead, we studied the o-C 6 H 4 + C 3 H 3 reaction in a resistively heated microtubular SiC reactor at controlled conditions of 1150 K and a pressure near 10–20 Torr. To this end, the reactants o-benzyne and propargyl were pyrolytically generated from benzoyl chloride and propargyl bromide. We identified the reactants and the indenyl radical isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). In conclusion, the experimentally observed predominant formation of indenyl radicals finally confirms the theoretical predictions of Matsugi and Miyoshi [Phys. Chem. Chem. Phys. 14 (2012), 9722–9728] and highlights a versatile route for the formation of five-membered rings and curved PAHs via reactions of o-benzyne that favor the formation of multiring species over aliphatically substituted aromatic species.

Molecular-weight growth↗

Matlab GUI for a Fluid Mixer

The Test and Engineering Directorate at NASA John C. Stennis Space Center developed an interest to study the modeling, evaluation, and control of a liquid hydrogen (LH2) and gas hydrogen (GH2) mixer subsystem of a ground test facility. This facility carries out comprehensive ground-based testing and certification of liquid rocket engines including the Space Shuttle Main engine. A software simulation environment developed in MATLAB/SIMULINK (M/S) will allow NASA engineers to test rocket engine systems at relatively no cost. In the progress report submitted in February 2004, we described the development of two foundation programs, a reverse look-up application using various interpolation algorithms, a variety of search and return methods, and self-checking methods to reduce the error in returned search results to increase the functionality of the program. The results showed that these efforts were successful. To transfer this technology to engineers who are not familiar with the M/S environment, a four-module GUI was implemented allowing the user to evaluate the mixer model under open-loop and closed-loop conditions. The progress report was based on an udergraduate Honors Thesis by Ms. Jamie Granger Austin in the Department of Electrical Engineering and Computer Science at Tulane University, during January-May 2003, and her continued efforts during August-December 2003. In collaboration with Dr. Hanz Richter and Dr. Fernando Figueroa we published these results in a NASA Tech Brief due to appear this year. Although the original proposal in 2003 did not address other components of the test facility, we decided in the last few months to extend our research and consider a related pressurization tank component as well. This report summarizes the results obtained towards a Graphical User Interface (GUI) for the evaluation and control of the hydrogen mixer subsystem model and for the pressurization tank each taken individually. Further research would combine the two components - mixer and tank, for a more realistic simulation tool.

Barbieri, Enrique↗

Room-temperature superconductivity in a carbonaceous sulfur hydride

One of the long-standing challenges in experimental physics is the observation of room-temperature superconductivity (RTSC). Recently, high temperature conventional superconductivity in hydrogen-rich materials has been reported in several systems under high pressure. The most significant discovery in reaching RTSC is the pressure-driven disproportionation of hydrogen sulfide (H 2 S) to H 3 S with a confirmed Tc of 203 kelvin at 155 gigapascals. As H 2 S readily mixes with hydrogen to form guest-host structures at lower pressures, the comparable size of methane to H 2 S should allow molecular exchange within a large assemblage of van der Waals solids that are (highly) hydrogen-rich with H 2 inclusions that are then the building blocks for novel superconducting compounds at extreme conditions. Here, we report superconductivity in a photochemically transformed carbonaceous sulfur hydride system with a maximum superconducting transition temperature of 287.7 ± 1.2 kelvin (~15° celsius) achieved at 267 ± 10 gigapascals. The superconducting state is observed over a broad pressure range from 140 to 275 gigapascals, with a dramatic upturn in Tc above 220 gigapascals. Superconductivity is established by the observation of zero resistance, magnetic susceptibility up to 190 gigapascals, and reduction of Tc under an external magnetic field up to 9 tesla, with an upper critical magnetic field of ~62 tesla based on Ginzburg–Landau (GL) model at zero temperature. The light, quantum nature of hydrogen limits structural and stoichiometric determination using x-ray scattering techniques. Raman spectroscopy is used to probe the chemical and structural transformations pre-metallization. In conclusion, the introduction of chemical tuning within our reported ternary system could be the path forward to lowering the pressure while preserving the RTSC properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multiparameter laser performance characterization of liquid crystals for polarization control devices in the nanosecond regime

Abstract Interactions of liquid crystals (LC’s) with polarized light have been studied widely and have spawned numerous device applications, including the fabrication of optical elements for high-power and large-aperture laser systems. Currently, little is known about both the effect of incident polarization state on laser-induced–damage threshold (LIDT) and laser-induced functional threshold (LIFT) behavior at sub-LIDT fluences under multipulse irradiation conditions. This work reports on the first study of the nanosecond-pulsed LIDT’s dependence on incident polarization for several optical devices employing oriented nematic and chiral-nematic LC’s oriented by surface alignment layers. Accelerated lifetime testing was also performed to characterize the ability of these devices to maintain their functional performance under multipulse irradiation as a function of the laser fluence at both 1053 nm and 351 nm. Results show that the LIDT varies as a function of input polarization by 30–80% within the same device, while the multipulse LIFT (which can differ from the nominal LIDT) depends on irradiation conditions such as laser fluence and wavelength.

47 OTHER INSTRUMENTATION↗

Tribological behavior of nuclear graphite in high-temperature inert environment

This report formally documents the completion of the Advanced Reactor Technologies Level 2 Milestone (M2AT-26OR0605058), “Complete initial wear/abrasion studies,” due June 1, 2026. The work presented in this report expend upon our previously published manuscript titled Sliding friction and wear behavior of nuclear graphite in high temperature inert environment: Influence of contact load, speed and temperature. The sliding friction and wear of self-mated ET-10 nuclear graphite were characterized across a range of elevated temperatures (650°C and 750°C), contact loads (20 N and 40 N), and sliding speeds (1 mm/s and 10 mm/s) within a controlled argon environment. Tribological data combined with advanced morphological characterization were used to provide a detailed mechanistic framework for the frictional and wear behavior of nuclear graphite in high-temperature inert conditions. Furthermore, the report evaluates the inherent limitations of bench-scale characterization and addresses the critical disparities between laboratory findings and the complex, in-service friction and wear behavior of fuel pebbles within a reactor environment.

36 MATERIALS SCIENCE↗

Chloride electrolyte enabled practical zinc metal battery with a near-unity Coulombic efficiency

Rechargeable aqueous zinc batteries are finding their niche in stationary storage applications where safety, cost, scalability and carbon footprint matter most. However, harnessing this reversible two-electron redox chemistry is plagued by major technical issues, notably hydrogen evolution reaction (HER) at the zinc surface, whose impacts are often not revealed under typical measurement conditions. Here we report a concentrated electrolyte design that eliminates this parasitic reaction and enables a Coulombic efficiency (CE) of 99.95% for Zn plating/stripping measured at a low current density of 0.2 mA cm -2 . With extra chloride salts and dimethyl carbonate in concentrated ZnCl 2 electrolyte, the hybrid electrolyte with a unique chemical environment features low Hammett acidity and facilitates the in situ formation of a dual-layered solid electrolyte interphase, protecting zinc anodes from HER and dendrite growth. Benefiting from the near-unity CE, the pouch cell with a VOPO 4 ·2H 2 O cathode sustains 500 deep cycles without swelling or leaking and delivers an energy density of 100 Wh kg -1 under practical conditions. Finally, our work represents a critical step forward in accelerating the market adoption of zinc batteries as an energy storage system with higher sustainability.

25 ENERGY STORAGE↗

Mafic explosive volcanism at Llaima Volcano: 3D x-ray microtomography reconstruction of pyroclasts to constrain shallow conduit processes

Abstract Mafic volcanic activity is dominated by effusive to mildly explosive eruptions. Plinian and ignimbrite-forming mafic eruptions, while rare, are also possible; however, the conditions that promote such explosivity are still being explored. Eruption style is determined by the ability of gas to escape as magma ascends, which tends to be easier in low-viscosity, mafic magmas. If magma permeability is sufficiently high to reduce bubble overpressure during ascent, volatiles may escape from the magma, inhibiting violent explosive activity. In contrast, if the permeability is sufficiently low to retain the gas phase within the magma during ascent, bubble overpressure may drive magma fragmentation. Rapid ascent may induce disequilibrium crystallization, increasing viscosity and affecting the bubble network with consequences for permeability, and hence, explosivity. To explore the conditions that promote strongly explosive mafic volcanism, we combine microlite textural analyses with synchrotron x-ray computed microtomography of 10 pyroclasts from the 12.6 ka mafic Curacautín Ignimbrite (Llaima Volcano, Chile). We quantify microlite crystal size distributions (CSD), microlite number densities, porosity, bubble interconnectivity, bubble number density, and geometrical properties of the porous media to investigate the role of magma degassing processes at mafic explosive eruptions. We use an analytical technique to estimate permeability and tortuosity by combing the Kozeny-Carman relationship, tortuosity factor, and pyroclast vesicle textures. The groundmass of our samples is composed of up to 44% plagioclase microlites, > 85% of which are < 10 µm in length. In addition, we identify two populations of vesicles in our samples: (1) a convoluted interconnected vesicle network produced by extensive coalescence of smaller vesicles (> 99% of pore volume), and (2) a population of very small and completely isolated vesicles (< 1% of porosity). Computed permeability ranges from 3.0 × 10 −13 to 6.3 × 10 −12 m 2 , which are lower than the similarly explosive mafic eruptions of Tarawera (1886; New Zealand) and Etna (112 BC; Italy). The combination of our CSDs, microlite number densities, and 3D vesicle textures evidence rapid ascent that induced high disequilibrium conditions, promoting rapid syn-eruptive crystallization of microlites within the shallow conduit. We interpret that microlite crystallization increased viscosity while simultaneously forcing bubbles to deform as they grew together, resulting in the permeable by highly tortuous network of vesicles. Using the bubble number densities for the isolated vesicles (0.1-3 −3 × 10 4 bubbles per mm 3 ), we obtain a minimum average decompression rate of 1.4 MPa/s. Despite the textural evidence that the Curacautín magma reached the percolation threshold, we propose that rapid ascent suppressed outgassing and increased bubble overpressures, leading to explosive fragmentation. Further, using the porosity and permeability of our samples, we estimated that a bubble overpressure > 5 MPa could have been sufficient to fragment the Curacautín magma. Other mafic explosive eruptions report similar disequilibrium conditions induced by rapid ascent rate, implying that syn-eruptive disequilibrium conditions may control the explosivity of mafic eruptions more generally.

Valdivia, Pedro↗

Upcycling mixed cathode materials to high-energy-density LiFe 0.75 Mn 0.25 PO 4

To address the demand for next-generation cathode materials with high energy density, upcycling LiFePO 4 into LiFe 0.75 Mn 0.25 PO 4 has attracted considerable attention. Nevertheless, existing strategies have yet to achieve both morphology and full elemental recovery under mild ambient conditions. Here, we report an upcycling route that can address this issue by combining leaching and a high-temperature treatment process. The upcycled LiFe 0.75 Mn 0.25 PO 4 exhibits enlarged lattice spacing and a high discharge plateau, and it delivers an energy density of 563.7 Wh/kg, 40.3 Wh/kg higher than recycled LiFePO 4 , which indicates the high value of the proposed upcycling strategy. At 1 C, LiFe 0.75 Mn 0.25 PO 4 also exhibits excellent cycling stability of 91% over 700 cycles. Techno-economic analysis also indicates impressive economic and environmental benefits, including 10.4% less raw materials usage and 12.2% less energy consumption and wastewater generation. This work demonstrates a scalable and economic upcycling strategy and provides a promising pathway for sustainable battery upcycling compatible with industrial conditions.

LMFP↗

Dust Abrasion Damage on Martian Solar Arrays: Experimental Investigation and Opportunity Rover Performance Analysis

Here we investigate the effects of erosion and weathering that occur on III-V cover-glass interconnected cells (CICs) after exposure to Mars dust storm conditions. The durability of these materials in a Martian environment is not well characterized so we perform analogous experimentation. To replicate the dust impingement, test coupons were placed in an enclosure and sandblasted with Mars dust simulant. We show the J-V response dependency on both incident angle and exposure times. We find that the simulated Martian dust storm often results in damage to the anti-reflective coating and subsequent reduced short circuit current. Reduction in the open circuit voltage is observed, likely caused by structural damage to the crystal lattice after CIC fracture. We employ data-driven modeling to determine a performance degradation rate that is consistent with zero within uncertainty. We also quantify the soiling contribution and power degradation of the photovoltaic cells on Mars through analysis of 4.95 Martian years of report-out power conditions from the Opportunity rover. We find that atmospheric dust suspended due to a weather event does not result in instantaneous settled dust on the PV cells. We calculate via autocorrelation function that the dust settling rate is approximately 21 Sols from atmospheric dust suspension. The findings presented here deliver a realistic approximation for the insolation values and subsequent PV power expected over time on the Martian surface thus informing future dust abatement systems.

McMillon-Brown, Lyndsey↗

Dust Abrasion Damage on Martian Solar Arrays: Experimental Investigation and Opportunity Rover Performance Analysis

Here we investigate the effects of erosion and weathering that occur on III-V cover-glass interconnected cells (CICs) after exposure to Mars dust storm conditions. The durability of these materials in a Martian environment is not well characterized so we perform analogous experimentation. To replicate the dust impingement, test coupons were placed in an enclosure and sandblasted with Mars dust simulant. We show the J-V response dependency on both incident angle and exposure times. We find that the simulated Martian dust storm often results in damage to the anti-reflective coating and subsequent reduced short circuit current. Reduction in the open circuit voltage is observed, likely caused by structural damage to the crystal lattice after CIC fracture. We employ data-driven modeling to determine a performance degradation rate that is consistent with zero within uncertainty. We also quantify the soiling contribution and power degradation of the photovoltaic cells on Mars through analysis of 4.95 Martian years of report-out power conditions from the Opportunity rover. We find that atmospheric dust suspended due to a weather event does not result in instantaneous settled dust on the PV cells. We calculate via autocorrelation function that the dust settling rate is approximately 21 Sols from atmospheric dust suspension. The findings presented here deliver a realistic approximation for the insolation values and subsequent PV power expected over time on the Martian surface thus informing future dust abatement systems.

McMillon-Brown, Lyndsey↗

Source and Chemistry of Hydroxymethanesulfonate (HMS) in Fairbanks, Alaska

Fairbanks, Alaska is a subarctic city with fine-particle (PM 2.5 ) concentrations that exceed air quality regulations in winter due to weak dispersion caused by strong atmospheric inversions, local emissions, and the unique chemistry occurring under the cold and dark conditions. Here we report on observations from the winters of 2020 and 2021, motivated by our pilot study which showed exceptionally high concentrations of fine particle hydroxy methane sulfonate (HMS) or related sulfur (IV) species (e.g., sulfite and bisulfite). We deployed an online Particle-Into-Liquid Sampler-Ion Chromatography (PILS-IC) in conjunction with a suite of instruments to determine HMS precursors (HCHO, SO 2 ) and aerosol composition in general, with the goal to characterize the sources and sinks of HMS in wintertime Fairbanks. PM 2.5 HMS comprised a significant fraction of PM 2.5 sulfur (26-41%) and overall PM 2.5 mass concentration (2.8-6.8%) during pollution episodes, substantially higher than what has been observed in other regions, likely due to the exceptionally low temperatures. HMS peaked in January, with lower concentrations in December and February, resulting from changes in precursors as well as meteorological conditions. Strong correlations with inorganic sulfate and organic mass during pollution events suggest HMS is linked to processes responsible for poor air quality episodes. These findings demonstrate unique aspects of air pollution formation in cold and humid atmospheres.

Fine-particle↗