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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 55 records · Page 3

Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe 0 ) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile-siderophile characteristics, where chalcophile-siderophile S served as a bridge to allow impregnating nFe 0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile-siderophile elements into the nFe 0 crystals are evidenced at both intraparticle and individual-particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity-selectivity-longevity-stability trade-off. Compared to nFe 0 , superhydrophobic Cu─S─nFe 0 with lattice expansion promoted dechlorination by 20-fold but inhibited HER by 150-fold, utilizing ≈80–100% electrons from the Fe 0 reservoir. This work demonstrates the concept of engineering nFe 0 lattice with tunable structure-property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integration of physiologically relevant photosynthetic energy flows into whole genome models of light‐driven metabolism

SUMMARY Characterizing photosynthetic productivity is necessary to understand the ecological contributions and biotechnology potential of plants, algae, and cyanobacteria. Light capture efficiency and photophysiology have long been characterized by measurements of chlorophyll fluorescence dynamics. However, these investigations typically do not consider the metabolic network downstream of light harvesting. By contrast, genome‐scale metabolic models capture species‐specific metabolic capabilities but have yet to incorporate the rapid regulation of the light harvesting apparatus. Here, we combine chlorophyll fluorescence parameters defining photosynthetic and non‐photosynthetic yield of absorbed light energy with a metabolic model of the pennate diatom Phaeodactylum tricornutum. This integration increases the model predictive accuracy regarding growth rate, intracellular oxygen production and consumption, and metabolic pathway usage. Through the quantification of excess electron transport, we uncover the sequential activation of non‐radiative energy dissipation processes, cross‐compartment electron shuttling, and non‐photochemical quenching as the rapid photoacclimation strategy in P. tricornutum. Interestingly, the photon absorption thresholds that trigger the transition between these mechanisms were consistent at low and high incident photon fluxes. We use this understanding to explore engineering strategies for rerouting cellular resources and excess light energy towards bioproducts in silico . Overall, we present a methodology for incorporating a common, informative data type into computational models of light‐driven metabolism and show its utilization within the design–build–test–learn cycle for engineering of photosynthetic organisms.

59 BASIC BIOLOGICAL SCIENCES↗

Feasibility study of common electronic equipment for shuttle sortie experiment payloads

A study was conducted to determine the feasibility of using standardized electronic equipment on the space shuttle vehicle in an effort to reduce the cost estimates. The standards for Nuclear Instrument Modules (NIM) and CAMAC electronic equipment are presented and described. It was determined that the CAMAC electronic equipment was more suitable for use with the space shuttle systems. Specific applications of the CAMAC equipment are analyzed. Illustrations of the equipment and circuit diagrams of the subsystems are provided.

Source record↗

Effect of Natural Organic Matter on the Fate of Cadmium During Microbial Ferrihydrite Reduction

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. In this work, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Furthermore, without NOM, only 3–4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mössbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controls on Iron Reduction and Biomineralization over Broad Environmental Conditions as Suggested by the Firmicutes Orenia metallireducens Strain Z6

Microbial iron reduction is a ubiquitous biogeochemical process driven by diverse microorganisms in a variety of environments. However, it is often difficult to separate the biological from the geochemical controls on bioreduction of Fe(III) oxides. In this study, we investigated the primary driving factor(s) that mediate secondary iron mineral formation over a broad range of environmental conditions using a single dissimilatory iron reducer, Orenia metallireducens strain Z6. A total of 17 distinct geochemical conditions were tested with differing pH (6.5–8.5), temperature (22–50 °C), salinity (2–20% NaCl), anions (phosphate and sulfate), electron shuttle (anthraquinone-2,6-disulfonate), and Fe(III) oxide mineralogy (ferrihydrite, lepidocrocite, goethite, hematite, and magnetite). The observed rates and extent of iron reduction differed significantly with k int between 0.186 and 1.702 mmol L –1 day –1 and Fe(II) production ranging from 6.3% to 83.7% of the initial Fe(III). Using X-ray absorption and scattering techniques (EXAFS and XRD), we identified and assessed the relationship between secondary minerals and the specific environmental conditions. It was inferred that the observed bifurcation of the mineralization pathways may be mediated by differing extents of Fe(II) sorption on the remaining Fe(III) minerals. These results expand our understanding of the controls on biomineralization during microbial iron reduction and aid the development of practical applications.

54 ENVIRONMENTAL SCIENCES↗

Combined Effects of Fe(III)-Bearing Clay Minerals and Organic Ligands on U(VI) Bioreduction and U(IV) Speciation

Reduction of U(VI) to U(IV) drastically reduces its solubility and has been proposed as a method for remediation of uranium contamination. However, much is still unknown about the kinetics, mechanisms, and products of U(VI) bioreduction in complex systems. In this work, U(VI) bioreduction experiments were conducted with Shewanella putrefaciens strain CN32 in the presence of clay minerals and two organic ligands: citrate and EDTA. In reactors with U and Fe(III)-clay minerals, the rate of U(VI) bioreduction was enhanced due to the presence of ligands, likely because soluble Fe 3+ - and Fe 2+ -ligand complexes served as electron shuttles. In the presence of citrate, bioreduced U(IV) formed a soluble U(IV)-citrate complex in experiments with either Fe-rich or Fe-poor clay mineral. In the presence of EDTA, U(IV) occurred as a soluble U(IV)-EDTA complex in Fe-poor montmorillonite experiments. However, U(IV) remained associated with the solid phase in Fe-rich nontronite experiments through the formation of a ternary U(IV)-EDTA-surface complex, as suggested by the EXAFS analysis. Our study indicates that organic ligands and Fe(III)-bearing clays can significantly affect the microbial reduction of U(VI) and the stability of the resulting U(IV) phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mediated Electrochemical Probing: A Systems-Level Tool for Redox Biology

Biology uses well-known redox mechanisms for energy harvesting (e.g., respiration), biosynthesis, and immune defense (e.g., oxidative burst), and now we know biology uses redox for systems-level communication. Currently, we have limited abilities to “eavesdrop” on this redox modality, which can be contrasted with our abilities to observe and actuate biology through its more familiar ionic electrical modality. In this Perspective, we argue that the coupling of electrochemistry with diffusible mediators (electron shuttles) provides a unique opportunity to access the redox communication modality through its electrical features. Here, we highlight previous studies showing that mediated electrochemical probing (MEP) can “communicate” with biology to acquire information and even to actuate specific biological responses (i.e., targeted gene expression). We suggest that MEP may reveal an extent of redox-based communication that has remained underappreciated in nature and that MEP could provide new technological approaches for redox biology, bioelectronics, clinical care, and environmental sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonadiabatic transitions in Landau-Zener grids: Integrability and semiclassical theory

We demonstrate that the general model of a linearly time-dependent crossing of two energy bands is integrable. Namely, the Hamiltonian of this model has a quadratically time-dependent commuting operator. We apply this property to four-state Landau-Zener (LZ) models that have previously been used to describe the Landau-Stückelberg interferometry experiments with an electron shuttling between two semiconductor quantum dots. The integrability then leads to simple but nontrivial exact relations for the transition probabilities. In addition, the integrability leads to a semiclassical theory that provides analytical approximation for the transition probabilities in these models for all parameter values. Lastly, the results predict a dynamic phase transition, and show that similarly looking models belong to different topological classes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Unlocking the distinctive enzymatic functions of the early plant biomass deconstructive genes in a brown rot fungus by cell-free protein expression

ABSTRACT Saprotrophic fungi that cause brown rot of woody biomass evolved a distinctive mechanism that relies on reactive oxygen species (ROS) to kick-start lignocellulosic polymers’ deconstruction. These ROS agents are generated at incipient decay stages through a series of redox relays that shuttle electrons from fungus’s central metabolism to extracellular Fenton chemistry. A list of genes has been suggested encoding the enzyme catalysts of the redox processes involved in ROS’s function. However, navigating the functions of the encoded enzymes has been challenging due to the lack of a rapid method for protein synthesis. Here, we employed cell-free expression system to synthesize four redox or degradative enzymes, which were identified, by transcriptomic data, as conserved players of the ROS oxidation phase across brown rot fungal species. All four enzymes were successfully expressed and showed activities that enable confident assignment of function, namely, benzoquinone reductase (BQR), ferric reductase, α-L-arabinofuranosidase (ABF), and heme-thiolate peroxidase (HTP). Detailed analysis of their catalytic features within the context of brown rot environments allowed us to interpret their roles during ROS-driven wood decomposition. Specifically, we validated the functions of BQR as the driver redox enzyme of Fenton cycles and reconstructed its interactions with the co-occurring HTP or laccase and ABF. Taken together, this research demonstrated that the cell-free expression platform is adequate for synthesizing functional fungal enzymes and provided an alternative route for the rapid characterization of fungal proteins, escalating our understanding of the distinctive biocatalyst system for plant biomass conversion. IMPORTANCE Brown rot fungi are efficient wood decomposers in nature, and their unique degradative systems harbor untapped catalysts pursued by the biorefinery and bioremediation industries. While the use of “omics” platforms has recently uncovered the key “oxidative-hydrolytic” mechanisms that allow these fungi to attack lignocellulose, individual protein characterization is lagging behind due to the lack of a robust method for rapid synthesis of crucial fungal enzymes. This work delves into the studies of biochemical functions of brown rot enzymes using a rapid, cell-free expression platform, which allowed the successful depictions of enzymes’ catalytic features, their interactions with Fenton chemistry, and their roles played during the incipient stage of brown rot when fungus sets off the reactive oxygen species for oxidative degradation. We expect this research could illuminate cell-free protein expression system’s use to fulfill the increasing need for functional studies of fungal enzymes, advancing the discoveries of novel biomass-converting catalysts.

60 APPLIED LIFE SCIENCES↗

Biogeochemical reactions and release of iron-bound organic carbon during the redox processes. Final report

Accurate simulation and prediction for reactions of soil organic carbon (OC) under different biogeochemical conditions remain a grand challenge. This project aims to investigate the transformation and degradation of OC under anaerobic and aerobic conditions as well as anaerobic-aerobic transitions, as well as its coupling with reactions for iron (Fe) oxide minerals. We determined that OC can serve as electron shuttle (including pyrogenic OC) and donor for accelerating the reduction of Fe oxide. The presence of OC can inhibit the transformation of poor crystalline Fe oxide (ferrihydrite) to other more crystalline forms. Reduction of Fe oxide can lead to the mobilization of OC, depending on the ratio of OC/Fe. More condensed aromatic OC can be selectively associated with Fe oxide and also resistant to the reduction release, enhancing their stability during the anaerobic reactions. Under aerobic condition, the association with Fe oxide can inhibit the degradation of OC and also its priming effects on the degradation of indigenous soil OC. During an anaerobic-aerobic transition, OC mineralization was inhibited substantially compared to controls incubated only aerobically. Our field measurement in the Arctic region revealed the importance of deep soil temperature in regulating the generation of CO 2 and CH 4 . These results highlighted the importance of redox reactions in controlling the fate and stability of soil OC. For future studies, investigations are required to fill in the knowledge gap regarding the structure and chemical nature of important organic ligands for Fe, accurate quantification of Fe-bound OC in soils, the long-term effects of anaerobic-aerobic transitions on the OC mineralization as well as response of microbial communities to redox transitions.

54 ENVIRONMENTAL SCIENCES↗

Carbon Utilization: Electrochemical Approach Using Novel Catalyst and System Integration

The environmental footprint from power generation can be mitigated by capturing emitted carbon dioxide (CO2) and converting it to value-added fuel sources. A multitude of different fuels can be produced from CO2 depending on the chemical reaction catalysts. Typically, these pathways can be developed electrochemically, or through hydrogenation. In recent years the electrochemical reduction of CO2 has grown exponentially, as it has shown potential to decrease atmospheric pollution and provide an additional means of on-demand electricity storage. Formic acid (FA) in particular has industrial applications such as in fuel cells or as a hydrogen storage medium, and requires a lower thermodynamic energy input than any other fuel produced for electrochemical CO2 reduction. However, product selectivity remains a challenge for conventional electrocatalysts, making FA production efficiencies above 50% difficult. To address the challenge of catalytic selectivity, UK CAER employs enzymatic catalysts to facilitate the FA production and minimize unwanted byproducts. Our process couples the catalyst with a charge mediator which is necessary to shuttle electrons, and an electrolyte pH buffer to prevent the catalyst from degrading. Presently, production efficiencies have approached 60% at a rate of over 10 mM FA/hour. System design considerations (flow rate, bulk volume) will also be discussed.

01 COAL, LIGNITE, AND PEAT↗

Microbial electro-photosynthesis

Methods and apparatus for growing photosynthetic organisms lacking Photosystem II (PSII) function using externally supplied electrons shuttled into the organism using redox mediators to improve photosynthetic output and to produce and recover chemicals of interest. By removing PSII, all PAR photons are funneled toward Photosystem I, thereby significantly increasing the theoretical photon utilization efficiency for CO2 fixation, energy storage and the capacity to synthesize valuable chemicals. Additional genetic modification can be performed to insert or enhance specific metabolic pathways to generate products of commercial interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigations for the improvement of space shuttle main engine electron beam welding equipment

Progress made in the testing, evaluation, and correction of MSFC's 7.5 kW electron beam welder in support of space shuttle main engine component welding is summarized. The objective of this project was to locate and correct the deficiencies in the welder. Some 17 areas were deficient in the 7.5 kW ERI welding system and the associated corrective action was taken to improve its operational performance. An overall improvement of 20 times the original reliability was obtained at full rated capacity after the modifications were made.

Smock, R. A.↗

Vehicle charging of the shuttle Orbiter during electron beam emission

The Vehicle Charging And Potential (VCAP) experiment has flown as part of shuttle missions STS-3/OSS-1 in March 1982 and STS-51F/Spacelab-2 in July/August 1985. During these missions, a 1 keV electron beam was emitted with currents of 50, 100 and 150 mA. The Orbiter response to electron beam emission was measured by a charge and current probe located in the payload bay. Examination of these vehicle charging and return current signatures has revealed a variety of unanticipated signatures in addition to several expected results. The principle results are listed and briefly discussed.

Hawkins, J. G.↗

Electron Transfer Beyond the Outer Membrane: Putting Electrons to Rest

Extracellular electron transfer (EET) is the physiological process that enables the reduction or oxidation of molecules and minerals beyond the surface of a microbial cell. The first bacteria characterized with this capability were Shewanella and Geobacter, both reported to couple their growth to the reduction of iron or manganese oxide minerals located extracellularly. A key difference between EET and nearly every other respiratory activity on Earth is the need to transfer electrons beyond the cell membrane. The past decade has resolved how well-conserved strategies conduct electrons from the inner membrane to the outer surface. However, recent data suggest a much wider and less well understood collection of mechanisms enabling electron transfer to distant acceptors. This review reflects the current state of knowledge from Shewanella and Geobacter, specifically focusing on transfer across the outer membrane and beyond—an activity that enables reduction of highly variable minerals, electrodes, and even other organisms.

59 BASIC BIOLOGICAL SCIENCES↗

Results from the Space Shuttle STS-95 Electronic Nose Experiment

A miniature electronic nose in which the sensing media are insulating polymers loaded with carbon black as a conductive medium has been designed and built at the Jet Propulsion Laboratory. The ENose has a volume of 1700 cc, weighs 1.4 kg including the operating computer, and uses 1.5 W average power (3 W peak power). This ENose was used in a demonstration experiment aboard STS-95 (October, 1998), in which the ENose was operated continuously for six days and recorded the sensors' response to the air in the middeck. The ENose was designed to detect ten common contaminants in space shuttle crew quarters air. The experiment was controlled by collecting air samples daily and analyzing them using standard analytical techniques after the flight. Changes in humidity were detected and quantified, neither the ENose nor the air samples detected any of the contaminants on the target list. The device is microgravity insensitive.

Ryan, M. A.↗