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At least 1,009 records · Page 56

Periodic domain boundary ordering in a dense molecular adlayer: Sub-saturation carbon monoxide on Pd(111)

Here, we describe a previously unreported ordered phase of carbon monoxide adsorbed on the (111) facet of single crystal palladium at near-saturation coverage. The adlayer superstructure is identified from low energy electron diffraction to be c(16×2) with respect to the underlying Pd(111) surface net. The ideal coverage is determined to be 0.6875 ML, approximately 92% of the 0.75–ML saturation coverage. Density functional theory calculations support a model for the molecular packing characterized by strips of locally-saturated (2×2) regions, with the CO bound near high-symmetry surface sites, separated by antiphase domain boundaries. The structure exists in a narrow coverage range and is prepared by heating the saturated adlayer to desorb a small fraction of the CO. Comparison of the c(16×2) domain-boundary structure with structural motifs at lower coverages suggests that between 0.6 and 0.6875 ML the adlayer order may be more strongly influenced by interadsorbate repulsion than by adsorption-site-specific interactions. The system is an example of the structural complexity that results from the compromise between adsorbate–substrate and adsorbate–adsorbate interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metabolism of Syringyl Lignin-Derived Compounds in Pseudomonas putida Enables Convergent Production of 2-Pyrone-4,6-Dicarboxylic Acid

Valorization of lignin, an abundant component of plant cell walls, is critical to enabling the lignocellulosic bioeconomy. Biological funneling using microbial biocatalysts has emerged as an attractive approach to convert complex mixtures of lignin depolymerization products to value-added compounds. Ideally, biocatalysts would convert aromatic compounds derived from the three canonical types of lignin: syringyl (S), guaiacyl (G), and p-hydroxyphenyl (H). Pseudomonas putida KT2440 (hereafter KT2440) has been developed as a biocatalyst owing in part to its native catabolic capabilities but is not known to catabolize S-type lignin-derived compounds. Here, we demonstrate that syringate, a common S-type lignin-derived compound, is utilized by KT2440 only in the presence of another energy source or when vanAB was overexpressed, as syringate was found to be O-demethylated to gallate by VanAB, a two-component monooxygenase, and further catabolized via extradiol cleavage. Unexpectedly, the specificity (kcat/KM) of VanAB for syringate was within 25% that for vanillate and O-demethylation of both substrates was well-coupled to O2 consumption. However, the native KT2440 gallate-cleaving dioxygenase, GalA, was potently inactivated by 3-O-methylgallate. To engineer a biocatalyst to simultaneously convert S-, G-, and H-type monomers, we therefore employed VanAB from Pseudomonas sp. HR199, which has lower activity for 3MGA, and LigAB, an extradiol dioxygenase able to cleave protocatechuate and 3-O-methylgallate. This strain converted 93% of a mixture of lignin monomers to 2-pyrone-4,6-dicarboxylate, a promising bio-based chemical. Overall, this study elucidates a native pathway in KT2440 for catabolizing S-type lignin-derived compounds and demonstrates the potential of this robust chassis for lignin valorization.

2-pyrone-4,6-dicarboxylic acid↗

Ecophysiology of an uncultivated lineage of Aigarchaeota from an oxic, hot spring filamentous ‘streamer’ community

In this study, the candidate archaeal phylum ‘Aigarchaeota’ contains microorganisms from terrestrial and subsurface geothermal ecosystems. The phylogeny and metabolic potential of Aigarchaeota has been deduced from several recent single-cell amplified genomes; however, a detailed description of their metabolic potential and in situ transcriptional activity is absent. Here, we report a comprehensive metatranscriptome-based reconstruction of the in situ metabolism of Aigarchaeota in an oxic, hot spring filamentous ‘streamer’ community. Fluorescence in situ hybridization showed that these newly discovered Aigarchaeota are filamentous, which is consistent with the presence and transcription of an actin-encoding gene. Aigarchaeota filaments are intricately associated with other community members, which include both bacteria (for example, filamentous Thermocrinis spp.) and archaea. Metabolic reconstruction of genomic and metatranscriptomic data suggests that this aigarchaeon is an aerobic, chemoorganoheterotroph with autotrophic potential. A heme copper oxidase complex was identified in the environmental genome assembly and highly transcribed in situ . Potential electron donors include acetate, fatty acids, amino acids, sugars and aromatic compounds, which may originate from extracellular polymeric substances produced by other microorganisms shown to exist in close proximity and/or autochthonous dissolved organic carbon (OC). Transcripts related to genes specific to each of these potential electron donors were identified, indicating that this aigarchaeon likely utilizes several OC substrates. Characterized members of this lineage cannot synthesize heme, and other cofactors and vitamins de novo , which suggests auxotrophy. We propose the name Candidatus ‘Calditenuis aerorheumensis’ for this aigarchaeon, which describes its filamentous morphology and its primary electron acceptor, oxygen.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis and use of a hyper-connecting cross-linking agent in the hole-transporting layer of perovskite solar cells

Solution-processed organic semiconducting materials feature prominently in modern optoelectronic devices, especially where low-cost and flexibility are specific goals, such as perovskite solar cells. Their intrinsic solubility, poor cohesion and lack of adhesion to underlying substrates, however, curtail their scope of application and durability. To overcome this, a mechanically stiff, light-activated, tetra-azide cross-linking agent, 1,3,5,7-tetrakis-(p-benzylazide)-adamantane (TPBA), has been developed to transform solution processed organic polymers into solvent-resistant and mechanically tough films. The use of 3-azidopropyltrimethoxysilane (AzPTMS) has been developed as a light-activated adhesion promotor, enabling mechanical testing of toughened, cross-linked polymers. Lithium bis(trifluoromethane)sulfonimide (LiTFSI) doped poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine, poly(triaryl amine) (PTAA), a hole-transporting material used in perovskite solar cells, has been selected as a candidate system for demonstrating the utility of TPBA to transform a fragile and highly-soluble hole-transporting organic semiconductor into a mechanically tough and solvent-resistant semiconducting composite. TPBA enables the solvent resistance and mechanical toughness of PTAA to be tuned without compromising the electronic functionality of the semiconducting material. Here, while increasing the fracture toughness of PTAA by over 300%, TPBA cross-linking also enables fabrication of perovskite solar cells with increased photovoltaic efficiencies in n–i–p and p–i–n geometries, and promotes adhesion of the doped polymer to the perovskite layer, mitigating interfacial device failure.

36 MATERIALS SCIENCE↗

Towards chloroplastic nanofactories: formation of proteinaceous scaffolds for metabolic engineering

The evolution of eukaryotic lipid-bound organelles allows for specialized metabolism to occur within spatially distinct metabolic landscapes within the same cell. However, this strategy of compartmentalization is not unique to eukaryotic organisms. Many bacteria, spread across 45 different phyla, contain loci that encode for specialized bacterial microcompartments (BMCs) (Sutter et al., 2021). The formation of a BMC involves self-assembly from three families of shell proteins to form the outer shell membrane, in addition to the encapsulation of an enzymatic core packaged within the lumen of a BMC (Kerfeld et al., 2018). These proteinaceous organelles provide a competitive growth advantage by enabling organisms to process inaccessible substrates by sequestering metabolic intermediates (i.e. aldehydes) that would otherwise be toxic within the cytoplasm. While BMCs perform specific metabolic functions in their native organism, synthetic, empty BMC shells can form without the requirement of native cargo inside (Doron and Kerfeld, 2024). This provides a transferable and tunable platform of protein scaffolding for guiding metabolic engineering within a host organism of choice (Raba and Kerfeld, 2022).

59 BASIC BIOLOGICAL SCIENCES↗

Diffusion-assisted molecular beam epitaxy of CuCrO 2 thin films

Using molecular beam epitaxy (MBE) to grow multielemental oxides (MEOs) is generally challenging, partly due to difficulty in stoichiometry control. Occasionally, if one of the elements is volatile at the growth temperature, stoichiometry control can be greatly simplified using adsorption-controlled growth mode. Otherwise, stoichiometry control remains one of the main hurdles to achieving high-quality MEO film growths. Here, in this paper, we report another kind of self-limited growth mode, dubbed diffusion-assisted epitaxy, in which excess species diffuses into the substrate and leads to the desired stoichiometry, in a manner similar to the conventional adsorption-controlled epitaxy. Specifically, we demonstrate that using diffusion-assisted epitaxy, high-quality epitaxial CuCrO 2 films can be grown over a wide growth window without precise flux control using MBE.

36 MATERIALS SCIENCE↗

Literature Review: Silicone Applications in Health Care

Early in the 20 th century, the term ‘silicone’ was coined by Professor Frederic Stanley Kipping, a British chemist and one of the founding fathers of silicon chemistry. The word was given to describe new compounds containing a Si-O linkage (siloxane bond) and basic chemical formula R 2 -Si-O. In industry, silicone usually refers to linear polydimethylsiloxane (PDMS), the most basic silicone polymer containing only methyl groups as substituents in the polymeric structure. However, the term silicone can also be used to describe complex polymer structures that feature a wide range of functional groups, branching or crosslinking. “The properties of basic PDMS materials can be changed by replacing some methyl groups with other organic groups or atoms.” Substitution of this type is useful when specific physical and chemical properties are required of the material, such as adhesion or compatibility with a certain substrate.

36 MATERIALS SCIENCE↗

Design of a Nanophotonic Hybrid Coupler

This project aims to design and simulate a nanophotonic hybrid coupler for detecting vacuum ultraviolet (VUV) light with higher efficiency. VUV light is of significant interest because of its applications ranging from high energy physics to space science and electronic industry. However, current VUV photodetectors have very low efficiencies because most materials absorb in the VUV region (100-200 nm). To address this challenge, I have designed a plasmonic-dielectric coupler with wavelength shifting properties, enabling high Purcell enhancement and far-field confinement. The coupler consists of a cylindrical cSi resonator on top of a thin ZnO layer, and Ag and SiO2 are used as substrates. Simulations are done using the finite-difference time domain method to solve Maxwell’s equations, and specifically with Meep and Lumerical. The effectiveness of the coupler is characterized by the Purcell factor and far-field radiation. The Purcell factor reaches a maximum near 390 nm and is in the o rder of 10^4. Furthermore, the coupler also allows partial control of the directionality of the far-field radiation. With the presence of the resonator, the radiation is directed towards the coupled metalens. Overall, our design combines the advantages of plasmonic and dielectric couplers, along with the intrinsic wavelength shifting properties of materials to enhance VUV detection significantly, and such a device can be used in, for example, the DUNE project.

Zhou, Jiayang↗

PIE-Enabled Study of Aqueous Corrosion & Zr Hydriding in Cr-Coated Cladding: M3GV-23PN0101132

Chromium-coated zirconium alloy cladding is under investigation as an accident-tolerant fuel (ATF) concept to extend performance to higher burnups via improved oxidation resistance and reduced hydrogen pickup. However, hydrothermal corrosion behavior and hydrogen transport mechanisms governing in-service hydriding of these coatings remain poorly understood. In a collaborative study between Pacific Northwest National Laboratory (PNNL), Idaho National Laboratory (INL), and the University of Huddersfield, cold spray (CS) and physical vapor deposition (PVD) Cr-coated Optimized ZIRLO™ cladding samples were characterized after exposure to PWR-simulated water chemistry under both in-core (neutron irradiation) and out-of-core (aqueous-only) conditions at the MIT Research Reactor. Multi-scale characterization was performed independently at PNNL and INL to evaluate coating integrity, microstructural evolution, Cr/Zr interface chemistry, and hydride formation. Both laboratories observed a consistent divergence in hydriding behavior: out-of-core CS Cr-coated cladding exhibited elevated hydride concentrations exceeding those of uncoated cladding, whereas in-core CS samples showed substantially suppressed hydriding. In-core specimens also displayed irradiation-specific features, including nanoscale voids within the Cr coating and radiation-induced segregation clusters in the Zr substrate. CS coatings retained an interdiffusion-free Cr/Zr bond with no intermetallic layer, whereas PVD coatings exhibited inferior quality with visible cracks and pores. An automated image-based hydride quantification method systematically overestimated bulk hydrogen content relative to inert gas fusion measurements, underscoring the need for standardized sample preparation and reference standards. Interpretation of hydride nucleation and growth is complicated by the open inner-diameter of the specimens, which provides additional hydrogen pathways. The results motivate further foundational studies to support predictive models of hydrothermal corrosion and hydrogen transport in unirradiated and irradiated Cr-coated cladding.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Enhancing Coherence Limits in Superconducting Quantum Systems for Computing and Sensing

This talk will highlight recent efforts at the SQMS Center to develop qudit-based quantum computing architectures using superconducting three-dimensional (3D) cavities, as well as the use of these ultra-coherent cavities for quantum sensing. I will present systematic studies of materials and devices aimed at identifying and mitigating the dominant sources of decoherence—including two-level systems (TLS), quasiparticles, and other noise mechanisms—in both transmons and 3D cavities. These investigations include microwave loss characterization of niobium, tantalum, aluminum, their native oxides, and substrate materials such as silicon and sapphire. By combining measurements on qubits and cavities, we disentangle subsystem-specific loss mechanisms and establish a hierarchy of mitigation strategies, leading to transmon coherence times exceeding one millisecond. I will also discuss studies of quasiparticle dynamics, including quasiparticle bursts observed in qubits operated both above ground and at the Gran Sasso underground laboratory, and the observation that applied magnetic fields can suppress temporal T₁ fluctuations. Building on these advances, we demonstrate a record-coherence two-cell cavity-qudit system with coherence times exceeding 20 milliseconds. Leveraging tunable sideband interactions together with error-resilient protocols, including measurement-based error correction and post-selection, we achieve high-fidelity quantum state control, including the preparation of Fock states up to N=20 with fidelities above 95% and the generation of high-fidelity two-mode entangled states. Finally, I will discuss how these ultra-coherent quantum systems are enabling emerging quantum sensing applications, including searches for dark matter and gravitational waves.

Roy, Tanay [Fermilab] (ORCID:000000019442862X)↗

Refurbishment of SRB aluminum components by walnut hull blast removal of protective coatings

A test program was conducted to develop, optimize, and scale up an abrasive blasting procedure was developed for refurbishment of specific SRB components: aft skirt, forward skirt, frustrum, and painted piece parts. Test specimens utilizing 2219 T87 aluminum substrate of varying thicknesses were prepared and blasted at progressively increasing pressures with selected abrasives. Specimens were analyzed for material response. The optimum blasting parameters were determined on panel specimens and verified on a large cylindrical integrated test bed.

Colberg, W. R.↗

An experimental study of growth and phase change of polar stratospheric cloud particles

This report describes the progress made on understanding phase changes related to solutions which may comprise Polar Stratospheric Clouds. In particular, it is concerned with techniques for investigating specific classes of metastability and phase change which may be important not only in Polar Stratospheric Clouds but in all atmospheric aerosols in general. While the lower level atmospheric aerosol consists of mixtures of (NH4)(SO4)2, NH4HSO4, NaCl among others, there is evidence that aerosol at PSC levels is composed of acid aerosol, either injected from volcanic events (such as Pinatubo) or having diffused upward from the lower atmosphere. In particular, sulfuric acid and nitric acid are known to occur at PSC levels, and are suspected of catalyzing ozone destruction reactions by adsorption on surfaces of crystallized particles. The present study has centered on two approaches: (1) the extent of supercooling (with respect to ice) and supersaturation (with respect to hydrate) and the nature of crystal growth in acid solutions of specific molality; and (2) the nature of growth from the vapor of HNO3 - H2O crystals both on a substrate and on a pre-existing aerosol.

Hallett, John↗

Current Developments in Future Planetary Probe Sensors for TPS

In-situ Thermal Protection System (TPS) sensors are required to provide traceability of TPS performance and sizing tools. Traceability will lead to higher fidelity design tools, which in turn will lead to lower design safety margins, and decreased heatshield mass. Decreasing TPS mass will enable certain missions that are not otherwise feasible, and directly increase science payload. NASA Ames is currently developing two flight measurements as essential to advancing the state of TPS traceability for material modeling and aerothermal simulation: heat flux and surface recession (for ablators). The heat flux gage is applicable to both ablators and non-ablators and is therefore the more generalized sensor concept of the two with wider applicability to mission scenarios. This paper describes the development of a microsensor capable of surface and in-depth temperature and heat flux measurements for TPS materials appropriate to Titan, Neptune, and Mars aerocapture, and direct entry. The thermal sensor will be monolithic solid state devices composed of thick film platinum RTD on an alumina substrate. Choice of materials and critical dimensions are used to tailor gage response, determined during calibration activities, to specific (forebody vs. aftbody) heating environments. Current design has maximum operating temperature of 1500 K, and allowable constant heat flux of q=28.7 watts per square centimeter, and time constants between 0.05 and 0.2 seconds. The catalytic and radiative response of these heat flux gages can also be changed through the use of appropriate coatings. By using several co-located gages with various surface coatings, data can be obtained to isolate surface heat flux components due to radiation, catalycity and convection. Selectivity to radiative heat flux is a useful feature even for an in-depth gage, as radiative transport may be a significant heat transport mechanism for porous TPS materials in Titan aerocapture. This paper also reports on progress to adapt a previously flown surface recession sensor, based on the Jupiter probe Galileo Analog Resistance Ablation Detector (ARAD), to appropriate aerocapture conditions.

Martinez, Ed↗

Development of Solid State Thermal Sensors for Aeroshell TPS Flight Applications

In-situ Thermal Protection System (TPS) sensors are required to provide verification by traceability of TPS performance and sizing tools. Traceability will lead to higher fidelity design tools, which in turn will lead to lower design safety margins, and decreased heatshield mass. Decreasing TPS mass will enable certain missions that are not otherwise feasible, and directly increase science payload. NASA Ames is currently developing two flight measurements as essential to advancing the state of TPS traceability for material modeling and aerothermal simulation: heat flux and surface recession (for ablators). The heat flux gage is applicable to both ablators and non-ablators and is therefore the more generalized sensor concept of the two with wider applicability to mission scenarios. This paper describes the continuing development of a thermal microsensor capable of surface and in-depth temperature and heat flux measurements for TPS materials appropriate to Titan, Neptune, and Mars aerocapture, and direct entry. The thermal sensor is a monolithic solid state device composed of thick film platinum RTD on an alumina substrate. Choice of materials and critical dimensions are used to tailor gage response, determined during calibration activities, to specific (forebody vs. aftbody) heating environments. Current design has maximum operating temperature of 1500K, and allowable constant heat flux of q=28.7 W/cm(sup 2), and time constants between 0.05 and 0.2 seconds. The catalytic and radiative response of these heat flux gages can also be changed through the use of appropriate coatings. By using several co-located gages with various surface coatings, data can be obtained to isolate surface heat flux components due to radiation, catalycity and convection. Selectivity to radiative heat flux is a useful feature even for an in-depth gage, as radiative transport may be a significant heat transport mechanism for porous TPS materials in Titan aerocapture.

Martinez, Ed↗

Probe Station and Near-Field Scanner for Testing Antennas

A facility that includes a probe station and a scanning open-ended waveguide probe for measuring near electromagnetic fields has been added to Glenn Research Center's suite of antenna-testing facilities, at a small fraction of the cost of the other facilities. This facility is designed specifically for nondestructive characterization of the radiation patterns of miniaturized microwave antennas fabricated on semiconductor and dielectric wafer substrates, including active antennas that are difficult to test in traditional antenna-testing ranges because of fragility, smallness, or severity of DC-bias or test-fixture requirements. By virtue of the simple fact that a greater fraction of radiated power can be captured in a near-field measurement than in a conventional far-field measurement, this near-field facility is convenient for testing miniaturized antennas with low gains.

Zaman, Afroz↗

Force-Measuring Clamps

Force-measuring clamps have been invented to facilitate and simplify the task of measuring the forces or pressures applied to clamped parts. There is a critical need to measure clamping forces or pressures in some applications for example, while bonding sensors to substrates or while clamping any sensitive or delicate parts. Many manufacturers of adhesives and sensors recommend clamping at specific pressures while bonding sensors or during adhesive bonding between parts in general. In the absence of a force-measuring clamp, measurement of clamping force can be cumbersome at best because of the need for additional load sensors and load-indicating equipment. One prior method of measuring clamping force involved the use of load washers or miniature load cells in combination with external power sources and load-indicating equipment. Calibrated spring clamps have also been used. Load washers and miniature load cells constitute additional clamped parts in load paths and can add to the destabilizing effects of loading mechanisms. Spring clamps can lose calibration quickly through weakening of the springs and are limited to the maximum forces that the springs can apply. The basic principle of a force-measuring clamp can be implemented on a clamp of almost any size and can enable measurement of a force of almost any magnitude. No external equipment is needed because the component(s) for transducing the clamping force and the circuitry for supplying power, conditioning the output of the transducers, and displaying the measurement value are all housed on the clamp. In other words, a force-measuring clamp is a complete force-application and force-measurement system all in one package. The advantage of unitary packaging of such a system is that it becomes possible to apply the desired clamping force or pressure with precision and ease.

Nunnelee, Mark↗

Virtual electrodes for high-density electrode arrays

The present embodiments are directed to implantable electrode arrays having virtual electrodes. The virtual electrodes may improve the resolution of the implantable electrode array without the burden of corresponding complexity of electronic circuitry and wiring. In a particular embodiment, a virtual electrode may include one or more passive elements to help steer current to a specific location between the active electrodes. For example, a passive element may be a metalized layer on a substrate that is adjacent to, but not directly connected to an active electrode. In certain embodiments, an active electrode may be directly coupled to a power source via a conductive connection. Beneficially, the passive elements may help to increase the overall resolution of the implantable array by providing additional stimulation points without requiring additional wiring or driver circuitry for the passive elements.

24 POWER TRANSMISSION AND DISTRIBUTION↗