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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 1,549 records · Page 86
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Rapid paper spray mass spectrometry characterization of uranium and exemplar molecular species

The ability to detect and quantify the presence of specific inorganic elements and complexes is essential for environmental monitoring and nuclear safeguards applications. In this work, paper spray ionization mass spectrometry (PSI–MS) was used for the rapid chemical and isotopic characterization of trace inorganic species collected on cotton swipe substrates. Here, the direct analysis of cotton swipes using this ambient ionization technique led to fast sample analysis that retained original chemical information of the source material with minimal sample preparation. Mass spectra were collected on an atmospheric pressure ionization, high–resolution mass spectrometer for solutions containing uranyl acetate, uranyl chloride, uranyl nitrate, and uranyl tri– n –butylphosphate (uranyl–TBP) complexes. Gadolinium nitrate was used as an internal standard for the quantitative analysis of uranium. To demonstrate the ability to characterize inorganic contaminants in the presence of uranium, a multi–element inorganic standard containing U, Bi, Pb, Cd, Fe, and Zn was deposited onto cotton substrates and directly analyzed without purification. All elements doped on the cotton substrate were detected with strong signal–to–noise (S/N) ratios (S/N~1000 for UO 2 + on multi–element doped swipes) and high integrated intensities (>10 5 counts) from collection periods of approximately 1 min. Limits of detection were determined to be approximately 94 ng for UO 2 + and uranyl acetate through the measurement of ppb level solutions. The rapid analysis of uranium and other inorganic–containing samples while still retaining original chemical information (e.g. uranyl complexation) was demonstrated. Qualitative detection and speciation were achieved in less than 1 min of analysis. For uranium isotopic quantitation, longer accumulations (>15 min) can be sustained to improve the accuracy of minor 235 U isotopic abundance measurements to approximately 1% error.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Tuning electronic properties in LaNiO 3 thin films by B-site Cu-substitution

Resistors are essential parts of futuristic all-oxide electronic architectures, yet easily overlooked due to their apparent simplicity. In this study, design of thin films with specific resistance spanning six orders of magnitude by partial substitution of Cu 2+ for Ni 3+ in the metallic conductor LaNiO 3 is shown. Substitution is attainable across the whole composition range using atomic layer deposition on LaAlO 3 (100) pc substrates, however with some inclusion of Ruddlesden–Popper RP1 phase (La 2 CuO 4 ) at high levels of Cu-incorporation. The thermal stability of the resistance is based on a metal–insulator transition that evolves from non-existent for LaNiO 3 to above room-temperature for high Cu 2+ substitution. This provides further insight in the metal–insulator transition found for correlated rare-earth nickelates, especially the type of transition seen for ultrathin films of LaNiO 3 that is usually attributed to oxygen vacancy formation. Materials with variable resistivity and metal–insulator-transition temperatures are key in the design of futuristic electronics such as metal–insulator-transition-driven neuromorphic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Quantifying cellulose accessibility during enzyme-mediated deconstruction using 2 fluorescence-tagged carbohydrate-binding modules

Two fluorescence-tagged carbohydrate-binding modules (CBMs), which specifically bind to crystalline (CBM2a-RRedX) and paracrystalline (CBM17-FITC) cellulose, were used to differentiate the supramolecular cellulose structures in bleached softwood Kraft fibers during enzyme-mediated hydrolysis. Differences in CBM adsorption were elucidated using confocal laser scanning microscopy (CLSM), and the structural changes occurring during enzyme-mediated deconstruction were quantified via the relative fluorescence intensities of the respective probes. It was apparent that a high degree of order (i.e., crystalline cellulose) occurred at the cellulose fiber surface, which was interspersed by zones of lower structural organization and increased cellulose accessibility. Quantitative image analysis, supported by 13 C NMR, scanning electron microscopy (SEM) imaging, and fiber length distribution analysis, showed that enzymatic degradation predominates at these zones during the initial phase of the reaction, resulting in rapid fiber fragmentation and an increase in cellulose surface crystallinity. By applying this method to elucidate the differences in the enzyme-mediated deconstruction mechanisms, this work further demonstrated that drying decreased the accessibility of enzymes to these disorganized zones, resulting in a delayed onset of degradation and fragmentation. The use of fluorescence-tagged CBMs with specific recognition sites provided a quantitative way to elucidate supramolecular substructures of cellulose and their impact on enzyme accessibility. By designing a quantitative method to analyze the cellulose ultrastructure and accessibility, this study gives insights into the degradation mechanism of cellulosic substrates.

09 BIOMASS FUELS↗
DOE OSTI2026

Sparsomycin inhibits translation through a conserved mechanism across all domains of life

Abstract Sparsomycin (SPA) is a broad-spectrum inhibitor of protein synthesis with activity across all three domains of life. Although SPA has long been known to target the ribosomal peptidyl transferase center (PTC), previous structural studies suggested that SPA binds differently to bacterial ribosomes compared to their archaeal and eukaryotic counterparts—an unexpected conclusion given the high evolutionary conservation of the ribosomal catalytic center. Here, we show that SPA inhibits a majority of elongation-competent bacterial ribosomal complexes and present X-ray crystal structures of Thermus thermophilus 70S ribosomes stalled by SPA at the initiation and early elongation stages of translation. These structures reveal that SPA binds to the bacterial ribosome in a manner essentially identical to that observed in archaeal and eukaryotic ribosomes, establishing a unified structural mechanism of SPA action across all domains of life. In this conserved binding mode, SPA occupies the A-site cleft of the PTC and forms an extensive network of interactions with universally conserved ribosomal RNA nucleotides and the CCA-end of the P-site transfer RNA (tRNA), thereby stabilizing the peptidyl-tRNA substrate while sterically blocking accommodation of an incoming aminoacyl-tRNA. By clarifying the mode of action of SPA on the bacterial ribosome, our work provides a structural framework for the rational design of SPA derivatives with improved potency and bacterial specificity.

Paranjpe, Madhura N [Department of Biological Scie↗
DOE OSTI2021

Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties

Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Technology Development for the Modification of High Aspect Ratio Geometries for Thermal and Environmental Control

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗
NASA NTRS2019

Application and Development of Atomic Layer Deposition Techniques to Improve Thermo-Optical Coatings for Spacecraft Thermal Control and Advanced Optical Instruments

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗
DOE OSTI2014

Gas sensitive materials for gas detection and methods of making

A gas sensitive material comprising SnO.sub.2 nanocrystals doped with In.sub.2O.sub.3 and an oxide of a platinum group metal, and a method of making the same. The platinum group metal is preferably Pd, but also may include Pt, Ru, Ir, and combinations thereof. The SnO.sub.2 nanocrystals have a specific surface of 7 or greater, preferably about 20 m2/g, and a mean particle size of between about 10 nm and about 100 nm, preferably about 40 nm. A gas detection device made from the gas sensitive material deposited on a substrate, the gas sensitive material configured as a part of a current measuring circuit in communication with a heat source.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Controlled Selective CVD Growth of ZnO Nanowires Enabled by Mask‐Free Fabrication Approach using Aqueous Fe Catalytic Inks

Abstract Fabrication process that enables selective growth of vertically oriented zinc oxide (ZnO) nanowires (NWs) via chemical vapor deposition method and mask‐free patterning approach is reported. It is shown that synthesis of high‐quality ZnO nanowires in various architectures is achievable by optimizing the growth conditions and by precise patterning of catalytic ink precursors. Parallel direct‐write patterning method is utilized to fabricate arrays of different architectures on Si/SiO 2 substrates and directly on devices at preselected locations. The production of high‐quality, crystalline ZnO NWs is demonstrated using aqueous iron catalytic inks. The composition of the ink and the lateral size of the patterns deposited on substrates are shown to affect the resulting nanowires and thus, allowing to control the geometry (length and diameter) of the individual ZnO NWs in the patterned assemblies. The results indicate that our protocols are tailored to the fabrication of ZnO NWs with specific surface geometries and interface functionalities for variety of targeted device applications.

Alameri, Dheyaa↗
DOE OSTI2014

Isopropanol production with engineered Cupriavidus necator as bioproduction platform

Alleviating our society's dependence on petroleum-based chemicals has been highly emphasized due to fossil fuel shortages and increasing greenhouse gas emissions. Isopropanol is a molecule of high potential to replace some petroleum-based chemicals, which can be produced through biological platforms from renewable waste carbon streams such as carbohydrates, fatty acids, or CO2. In this study, for the first time, the heterologous expression of engineered isopropanol pathways were evaluated in a Cupriavidus necator strain Re2133, which was incapable of producing poly-3-hydroxybutyrate [P(3HB)]. These synthetic production pathways were rationally designed through codon optimization, gene placement, and gene dosage in order to efficiently divert carbon flow from P(3HB) precursors toward isopropanol. Among the constructed pathways, Re2133/pEG7c overexpressing native C. necator genes encoding a beta-ketothiolase, a CoA-transferase, and codon-optimized Clostridium genes encoding an acetoacetate decarboxylase and an alcohol dehydrogenase produced up to 3.44 g l(-1) isopropanol in batch culture, from fructose as a sole carbon source, with only 0.82 g l(-1) of biomass. The intrinsic performance of this strain (maximum specific production rate 0.093 g g(-1) h(-1), yield 0.32 Cmole Cmole(-1)) corresponded to more than 60 % of the respective theoretical performance. Moreover, the overall isopropanol production yield (0.24 Cmole Cmole(-1)) and the overall specific productivity (0.044 g g(-1) h(-1)) were higher than the values reported in the literature to date for heterologously engineered isopropanol production strains in batch culture. Strain Re2133/pEG7c presents good potential for scale-up production of isopropanol from various substrates in high cell density cultures.

Grousseau, E↗
DOE OSTI2020

Exploration of Sn 70 Li 30 alloy as possible material for flowing liquid metal plasma facing components

As an advanced alternative to solid materials, Liquid Metals (LM) may offer more resilient and feasible Plasma Facing Components (PFCs). Particularly, regarding the unavoidable material erosion/degradation produced by particle/heat fluxes in future fusion devices where much longer duty cycles are expected. Furthermore, configurations that propose a flowing LM surface can add the advantage of a continuously fresh and clean layer facing the plasma. Although lithium is the most widely tested option, tin-lithium (SnLi) alloys have been proposed to attempt to combine the positive characteristics of both pure elements and ameliorate the specific issues of lithium. In this work, the potential use of Sn70Li30 alloy in such flowing concepts has been explored by addressing several preliminary and mandatory aspects for its utilization. Key issues such as wettability and compatibility of the alloy with relevant substrates have been studied in a multidisciplinary approach. The data obtained from deposited liquid tin-lithium droplets indicates approximate wetting temperatures of 360 °C, 390 °C and 405 °C for the fresh alloy on 316 stainless steel, molybdenum, and tungsten, respectively. However, the alloy contamination appeared to strongly affect the wetting characteristics of materials, increasing their wetting temperature by ~130 °C in the worst observed cases. Interestingly, in some instances, the instability of the liquid alloy surface was observed in the form of sudden gaseous ejection. The deposited droplets were posteriorly characterized in terms of absolute composition and depth profile by Inductively Coupled PlasmaOptical Emission Spectroscopy (ICP-OES) and Secondary Ion Mass Spectrometry (SIMS-ToF). Additionally, the nature and composition of the boundaries between the substrates and alloy microparticles was investigated by Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), and 3D Laser microscopy. The overall results of this post-mortem characterization revealed that first signs of corrosion induced by both alloy elements (lithium-chromium association and iron-tin intermetallic mixing) were present on 316 stainless steel after short exposures (≤3 h) at temperatures lower than 550 °C. Conversely, molybdenum and tungsten showed good compatibility with the alloy in equivalent conditions. The global implications of these results are finally addressed, focusing on the future perspectives and the more viable scenarios for the eventual utilization of these alloys in flowing liquid metal configurations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

The effects of warming and soil chemistry on bacterial community structure in Arctic tundra soils

Soil microbial communities in the Arctic play a critical role in regulating the global carbon (C) cycle. Vast amounts of C are stored in northern latitude soils, and rising temperatures in the Arctic threaten to thaw permafrost, making relatively inaccessible C sources more available for mineralization by soil microbes. Few studies have characterized how microbial community structure responds to thawing permafrost in the context of varying soil chemistries associated with contrasting tundra landscapes. Here, we subjected active layer and permafrost soils from upland and lowland tundra sites on the North Slope of Alaska to a soil-warming incubation experiment and compared soil bacterial community profiles (obtained by 16S rRNA amplicon sequencing) before and after incubation. The influence of soil composition (characterized by mid-infrared [MIR] spectroscopy) on bacterial community structure and class abundance was analyzed using redundancy and correlation analyses. We found increased abundances of Alphaproteobacteria, Gammaproteobacteria, and Bacteroidetes [Sphingobacteriia] post incubation, particularly in permafrost soils. The categorical descriptors site and soil layer had the most explanatory power in our predictive models of bacterial community structure, highlighting the close relationship between soil bacteria and the soil environment. Specific soil chemical attributes characterizing the soil environments that were found to be the best predictors include MIR spectral bands associated with inorganic C, silicates, amide II (C=N stretch), and carboxylics (C-O stretch), and MIR peak ratios representing C substrate quality. Overall, these results further characterize soil bacterial community shifts that may occur as a frozen environment with limited access to C sources, such as is found in undisturbed permafrost, transitions to warmer and more C-available environments, such as is predicted in thawing permafrost due to climate change.

16S rRNA sequencing↗
DOE OSTI2013

Microbial diversity and dynamics during methane production from municipal solid waste

Highlights: ► Similar bacterial communities developed following different start-up operation. ► Total methanogens in leachate during the decelerated methane phase reflected overall methane yield. ► Created correlations between methanogens, methane yield, and available substrate. ► Predominant bacteria identified with syntrophic polysaccharide degraders. ► Hydrogenotrophic methanogens were dominant in the methane generation process. - Abstract: The objectives of this study were to characterize development of bacterial and archaeal populations during biodegradation of municipal solid waste (MSW) and to link specific methanogens to methane generation. Experiments were conducted in three 0.61-m-diameter by 0.90-m-tall laboratory reactors to simulate MSW bioreactor landfills. Pyrosequencing of 16S rRNA genes was used to characterize microbial communities in both leachate and solid waste. Microbial assemblages in effluent leachate were similar between reactors during peak methane generation. Specific groups within the Bacteroidetes and Thermatogae phyla were present in all samples and were particularly abundant during peak methane generation. Microbial communities were not similar in leachate and solid fractions assayed at the end of reactor operation; solid waste contained a more abundant bacterial community of cellulose-degrading organisms (e.g., Firmicutes). Specific methanogen populations were assessed using quantitative polymerase chain reaction. Methanomicrobiales, Methanosarcinaceae, and Methanobacteriales were the predominant methanogens in all reactors, with Methanomicrobiales consistently the most abundant. Methanogen growth phases coincided with accelerated methane production, and cumulative methane yield increased with increasing total methanogen abundance. The difference in methanogen populations and corresponding methane yield is attributed to different initial cellulose and hemicellulose contents of the MSW. Higher initial cellulose and hemicellulose contents supported growth of larger methanogen populations that resulted in higher methane yield.

09 BIOMASS FUELS↗
DOE OSTI2017

Substitution of Aromatic Residues with Polar Residues in the Active Site Pocket of epi -Isozizaene Synthase Leads to the Generation of New Cyclic Sesquiterpenes

The sesquiterpene cyclase epi-isozizaene synthase (EIZS) catalyzes the cyclization of farnesyl diphosphate to form the tricyclic hydrocarbon precursor of the antibiotic albaflavenone. The hydrophobic active site pocket of EIZS serves as a template as it binds and chaperones the flexible substrate and carbocation intermediates through the conformations required for a multistep reaction sequence. We previously demonstrated that the substitution of hydrophobic residues with other hydrophobic residues remolds the template and expands product chemodiversity. Here, we show that the substitution of hydrophobic residues—specifically, Y69, F95, F96, and W203—with polar side chains also yields functional enzyme catalysts that expand product chemodiversity. Fourteen new EIZS mutants are reported that generate product arrays in which eight new sesquiterpene products have been identified. Of note, some mutants generate acyclic and cyclic hydroxylated products, suggesting that the introduction of polarity in the hydrophobic pocket facilitates the binding of water capable of quenching carbocation intermediates. Furthermore, the substitution of polar residues for F96 yields high-fidelity sesquisabinene synthases. Crystal structures of selected mutants reveal that residues defining the three-dimensional contour of the hydrophobic pocket can be substituted without triggering significant structural changes elsewhere in the active site. Finally, more radical nonpolar–polar amino acid substitutions should be considered when terpenoid cyclase active sites are remolded by mutagenesis with the goal of exploring and expanding product chemodiversity.

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

Derivation of Multiple Covarying Material and Process Parameters Using Physics-Based Modeling of X-ray Data

There is considerable interest in developing multimodal characterization frameworks capable of probing critical properties of complex materials by relying on distinct, complementary methods or tools. Any such framework should maximize the amount of information that is extracted from any given experiment and should be sufficiently powerful and efficient to enable on-the-fly analysis of multiple measurements in a self-consistent manner. Such a framework is demonstrated in this work in the context of self-assembling polymeric materials, where theory and simulations provide the language to seamlessly mesh experimental data from two different scattering measurements. Specifically, the samples considered here consist of diblock copolymers (BCP) that are self-assembled on chemically nanopatterned surfaces. The copolymers microphase separate into ordered lamellae with characteristic dimensions on the scale of tens of nanometers that are perfectly aligned by the substrate over macroscopic areas. These aligned lamellar samples provide ideal standards with which to develop the formalism introduced in this work and, more generally, the concept of high-information-content, multimodal experimentation. In conclusion, the outcomes of the proposed analysis are then compared to images generated by 3D scanning electron microscopy tomography, serving to validate the merit of the framework and ideas proposed here.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Polysaccharide utilization loci of North Sea Flavobacteriia as basis for using SusC/D-protein expression for predicting major phytoplankton glycans

Marine algae convert a substantial fraction of fixed carbon dioxide into various polysaccharides. Flavobacteriia that are specialized on algal polysaccharide degradation feature genomic clusters termed polysaccharide utilization loci (PULs). As knowledge on extant PUL diversity is sparse, we sequenced the genomes of 53 North Sea Flavobacteriia and obtained 400 PULs. Bioinformatic PUL annotations suggest usage of a large array of polysaccharides, including laminarin, α-glucans, and alginate as well as mannose-, fucose-, and xylose-rich substrates. Many of the PULs exhibit new genetic architectures and suggest substrates rarely described for marine environments. The isolates’ PUL repertoires often differed considerably within genera, corroborating ecological niche-associated glycan partitioning. Polysaccharide uptake in Flavobacteriia is mediated by SusCD-like transporter complexes. Respective protein trees revealed clustering according to polysaccharide specificities predicted by PUL annotations. Using the trees, we analyzed expression of SusC/D homologs in multiyear phytoplankton bloom-associated metaproteomes and found indications for profound changes in microbial utilization of laminarin, αglucans, β-mannan, and sulfated xylan. We hence suggest the suitability of SusC/D-like transporter protein expression within heterotrophic bacteria as a proxy for the temporal utilization of discrete polysaccharides.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Controlled monodefluorination and alkylation of C(sp 3 )–F bonds by lanthanide photocatalysts: importance of metal–ligand cooperativity

The controlled functionalization of a single fluorine in a CF 3 group is difficult and rare. Photochemical C–F bond functionalization of the sp 3 -C–H bond in trifluorotoluene, PhCF 3 , is achieved using catalysts made from earth-abundant lanthanides, (Cp Me4 ) 2 Ln(2-O-3,5- t Bu 2 -C 6 H 2 )(1-C{N(CH) 2 N( i Pr)}) (Ln = La, Ce, Nd and Sm, Cp Me4 = C 5 Me 4 H). The Ce complex is the most effective at mediating hydrodefluorination and defluoroalkylative coupling of PhCF 3 with alkenes; addition of magnesium dialkyls enables catalytic C–F bond cleavage and C–C bond formation by all the complexes. Mechanistic experiments confirm the essential role of the Lewis acidic metal and support an inner-sphere mechanism of C–F activation. Computational studies agree that coordination of the C–F substrate is essential for C–F bond cleavage. The unexpected catalytic activity for all members is made possible by the light-absorbing ability of the redox non-innocent ligands. The results described herein underscore the importance of metal–ligand cooperativity, specifically the synergy between the metal and ligand in both light absorption and redox reactivity, in organometallic photocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗