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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Probing sulphur clusters in a microfluidic electrochemical cell with synchrotron-based photoionization mass spectrometry

We present synchrotron-based mass spectrometry to probe products formed in the lithium sulphide electrolyte. In operando analysis was obtained at two different potentials in a vacuum compatible microfluidic electrochemical cell. Mass spectral observations show that the charged electrolyte formed sulfur clusters under dynamic conditions, demonstrating electrolyte electron shuttling.

sulphur cluster, lithium – sulphur battery electro↗
NASA NTRS1991

A simulation study of interactions of Space-Shuttle generated electron beams with ambient plasma and neutral gas

The object was to conduct large scale simulations of electron beams injected into space. The study of active injection of electron beams from spacecraft is important since it provides valuable insight into beam-plasma interactions and the development of current systems in the ionosphere. However, the beam injection itself is not simple, being constrained by the ability of the spacecraft to draw return current from the ambient plasma. The generation of these return currents is dependent on several factors, including the density of the ambient plasma relative to the beam density, the presence of neutrals around the spacecraft, the configuration of the spacecraft, and the motion of the spacecraft through the plasma. Two dimensional particle simulations with collisional processes included are used to show how these different and often coupled processes can be utilized to enhance beam propagation from the spacecraft. To understand the radical expansion of mechanism of an electron beam from a highly charged spacecraft, two dimensional particle in cell simulations were conducted for a high density electron beam injected parallel to magnetic fields from an isolated equipotential conductor into a cold background plasma. The simulations indicate that charge buildup at the beam stagnation point causes the beam to expand radially to the beam electron gyroradius.

Source record↗
NASA NTRS1991

A simulation study of interactions of space-shuttle generated electron beams with ambient plasma and neutral gas

The objective was to conduct large scale simulations of electron beams injected into space. The study of the active injection of electron beams from spacecraft is important, as it provides valuable insight into the plasma beam interactions and the development of current systems in the ionosphere. However, the beam injection itself is not simple, being constrained by the ability of the spacecraft to draw current from the ambient plasma. The generation of these return currents is dependent on several factors, including the density of the ambient plasma relative to the beam density, the presence of neutrals around the spacecraft, the configuration of the spacecraft, and the motion of the spacecraft through the plasma. Two dimensional (three velocity) particle simulations with collisional processes included are used to show how these different and often coupled processes can be used to enhance beam propagation from the spacecraft. To understand the radial expansion mechanism of an electron beam injected from a highly charged spacecraft, two dimensional particle-in-cell simulations were conducted for a high density electron beam injected parallel to magnetic fields from an isolated equipotential conductor into a cold background plasma. The simulations indicate that charge build-up at the beam stagnation point causes the beam to expand radially to the beam electron gyroradius.

Winglee, Robert M.↗
NASA NTRS1992

Simulation study of interactions of Space Shuttle-generated electron beams with ambient plasmas

This report summarizes results obtained through the support of NASA Grant NAGW-1936. The objective of this report is to conduct large scale simulations of electron beams injected into space. The topics covered include the following: (1) simulation of radial expansion of an injected electron beam; (2) simulations of the active injections of electron beams; (3) parameter study of electron beam injection into an ionospheric plasma; and (4) magnetosheath-ionospheric plasma interactions in the cusp.

Lin, Chin S.↗
DOE OSTI2021

SPRUCE Warming Promotes the Use of Organic Matter as an Electron Acceptor in a Peatland: Supporting Data

These data are provided in support of the publication: Warming Promotes the Use of Organic Matter as an Electron Acceptor in a Peatland (Rush et al., 2021). Rush et al. (2021) reported on the effect of temperature on microbial organic matter reduction at the SPRUCE study site and S1 bog. Specifically, electron shuttling capacity (ESC), CH4 production, CO2 production, and acetate concentration were measured to explore both direct and indirect (through changes in soil quality and water-table level) effects of warming on microbial activity. Samples were collected in the summer of 2016 and 2017 depending on the experiment. This dataset contains five files in comma separated (*.csv) format. The SPRUCE Experiment Site is located in a Picea mariana [black spruce] Sphagnum spp. bog forest in northern Minnesota, 40 km north of Grand Rapids, in the USDA Forest Service Marcell Experimental Forest (MEF). This ecosystem, which is located at the southern margin of the boreal forest, is considered especially vulnerable to climate change and anticipated to be near its tipping point.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

SPRUCE Redox-Active Subsurface Organic Matter, Marcell Experimental Forest, Minnesota, 2023

This dataset contains measurements that report on the effects of the SPRUCE experimental treatments on redox-active organic matter (RAOM) reduction (Valenzuela and Cervantes, 2021). Measurements occurred at the SPRUCE Experiment site in the Marcell Experimental Forest in northern Minnesota, USA. This work is also a follow-up to Rush et al. (2021a) which investigated effects of temperature on RAOM reduction after two years of experimental warming (Rush et al. 2021b). This follow-up dataset addresses two main questions; (i) How does warming and elevated carbon dioxide (CO2) directly affect in situ RAOM reduction, and subsequent methane (CH4) and CO2 production, across the peat depth profile? and (ii) How has long-term warming and elevated CO2 changed the total RAOM pool, and subsequent CH4 and CO2 production, across the peat depth profile? This dataset reports electron shuttling capacity (a proxy for RAOM reduction; Keller, and Takagi, 2013) and carbon dioxide (CO2) and methane (CH4) concentrations both in one-week in situ incubations (2023-05-31 to 2023-08-01) and 42-day laboratory incubations from peat collected in 2023 (2023-05-31 to 2023-06-26). Laboratory incubations also measured acetate concentrations. The 2023 laboratory incubations were also compared with laboratory incubations conducted on peat collected in 2016 (Rush et al. 2021b). This dataset contains three data files in comma-separate (.csv) format. Additional metadata are provided: three data dictionaries and a file-level metadata file in comma separate (.csv) format and a user guide in PDF (*.pdf) format.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Single-Molecule Detection of the Encounter and Productive Electron Transfer Complexes of a Photosynthetic Reaction Center

Small, diffusible redox proteins play an essential role in electron transfer (ET) in respiration and photosynthesis, sustaining life on Earth by shuttling electrons between membrane-bound complexes via finely tuned and reversible interactions. Ensemble kinetic studies show transient ET complexes form in two distinct stages: an “encounter” complex largely mediated by electrostatic interactions, which subsequently, through subtle reorganization of the binding interface, forms a “productive” ET complex stabilized by additional hydrophobic interactions around the redox-active cofactors. Here, using single-molecule force spectroscopy (SMFS) we dissected the transient ET complexes formed between the photosynthetic reaction center-light harvesting complex 1 (RC-LH1) of Rhodobacter sphaeroides and its native electron donor cytochrome c 2 (cyt c 2 ). Importantly, SMFS resolves the distribution of interaction forces into low (~150 pN) and high (~330 pN) components, with the former more susceptible to salt concentration and to alteration of key charged residues on the RC. Thus, the low force component is suggested to reflect the contribution of electrostatic interactions in forming the initial encounter complex, whereas the high force component reflects the additional stabilization provided by hydrophobic interactions to the productive ET complex. Employing molecular dynamics simulations, we resolve five intermediate states that comprise the encounter, productive ET and leaving complexes, predicting a weak interaction between cyt c 2 and the LH1 ring near the RC-L subunit that could lie along the exit path for oxidized cyt c 2 . The multimodal nature of the interactions of ET complexes captured here may have wider implications for ET in all domains of life.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Amino Acid Residues Controlling Domain Interaction and Interdomain Electron Transfer in Cellobiose Dehydrogenase

The function of cellobiose dehydrogenase (CDH) in biosensors, biofuel cells, and as a physiological redox partner of lytic polysaccharide monooxygenase (LPMO) is based on its role as an electron donor. Before donating electrons to LPMO or electrodes, an interdomain electron transfer from the catalytic FAD-containing dehydrogenase domain to the electron shuttling cytochrome domain of CDH is required. This study investigates the role of two crucial amino acids located at the dehydrogenase domain on domain interaction and interdomain electron transfer by structure-based engineering. The electron transfer kinetics of wild-type Myriococcum thermophilum CDH and its variants M309A, R698S, and M309A/R698S were analyzed by stopped-flow spectrophotometry and structural effects were studied by small-angle X-ray scattering. The data show that R698 is essential to pull the cytochrome domain close to the dehydrogenase domain and orient the heme propionate group towards the FAD, while M309 is an integral part of the electron transfer pathway – its mutation reducing the interdomain electron transfer 10-fold. Structural models and molecular dynamics simulations pinpoint the action of these two residues on the domain interaction and interdomain electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exogenous electricity flowing through cyanobacterial photosystem I drives CO 2 valorization with high energy efficiency

Nature's biocatalytic processes are driven by photosynthesis, whereby photosystems I and II are connected in series for light-stimulated generation of fuel products or electricity. Externally supplying electricity directly to the photosynthetic electron transfer chain (PETC) has numerous potential benefits, although strategies for achieving this goal have remained elusive. Here we report an integrated photo-electrochemical architecture which shuttles electrons directly to PETC in living cyanobacteria. The cathode of this architecture electrochemically interfaces with cyanobacterial cells that have a lack of photosystem II activity and cannot perform photosynthesis independently. Illumination of the cathode channels electrons from an external circuit to intracellular PETC through photosystem I, ultimately fueling cyanobacterial conversion of CO 2 into acetate. We observed acetate formation when supplying both illumination and exogenous electrons under intermittent conditions (e.g., in a 30 s supply plus 30 min interval condition of both light and exogenous electrons). The energy conversion efficiency for acetate production under programmed intermittent LED illumination (400–700 nm) and exogenous electron supply reached ca. 9%, when taking into account the number of photons and electrons received by the biotic system, and ca. 3% for total photons and electrons supplied to the cyanobacteria. This approach is applicable for generating various CO 2 reduction products by using engineered cyanobacteria, one of which has enabled electrophototrophic production of ethylene, a broadly used hydrocarbon in the chemical industry. The resulting bio-electrochemical hybrid has the potential to produce fuel chemicals with numerous potential advantages over standalone natural and artificial photosynthetic approaches.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1984

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗
NASA NTRS1985

Measured electron contribution to Shuttle plasma environment: Abbreviated update

The differential energy spectra of electrons between 1 and 100 eV were measured by an electron spectrometer flown on an early shuttle. This energy range was scanned in 64 incremental steps with a resolution of 7%. The most striking feature that was observed throughout these spectra was a relatively flat distribution of the higher energy electrons out to 100 eV. This is in contrast to normal ambient spectra which consistently show a rapid decline in quantitative flux beyond 50 to 55 eV. The lower energy (1 to 2 eV) end of these spectra showed steep thermal trails comparable to normal ambient spectral structure. In general, daytime fluxes were significantly higher than those obtained during nighttime measurements. Quantitative flux excursions which may possibly be associated with thruster firing were frequently observed. Spectral structure suggestive of the N2 vibrational excitation energy loss mechanism was also seen in the data from some measurement periods. Examples of these spectra are shown and possible correlations are discussed.

Mcmahon, W.↗
DOE OSTI2021

Effects of Fe(III) Oxide Mineralogy and Phosphate on Fe(II) Secondary Mineral Formation during Microbial Iron Reduction

The bioreduction of Fe(III) oxides by dissimilatory iron-reducing bacteria may result in the formation of a suite of Fe(II)-bearing secondary minerals, including magnetite (a mixed Fe(II)/Fe(III) oxide), siderite (Fe(II) carbonate), vivianite (Fe(II) phosphate), chukanovite (ferrous hydroxy carbonate), and green rusts (mixed Fe(II)/Fe(III) hydroxides). In an effort to better understand the factors controlling the formation of specific Fe(II)-bearing secondary minerals, we examined the effects of Fe(III) oxide mineralogy, phosphate concentration, and the availability of an electron shuttle (9,10-anthraquinone-2,6-disulfonate, AQDS) on the bioreduction of a series of Fe(III) oxides (akaganeite, feroxyhyte, ferric green rust, ferrihydrite, goethite, hematite, and lepidocrocite) by Shewanella putrefaciens CN32, and the resulting formation of secondary minerals, as determined by X-ray diffraction, Mössbauer spectroscopy, and scanning electron microscopy. The overall extent of Fe(II) production was highly dependent on the type of Fe(III) oxide provided. With the exception of hematite, AQDS enhanced the rate of Fe(II) production; however, the presence of AQDS did not always lead to an increase in the overall extent of Fe(II) production and did not affect the types of Fe(II)-bearing secondary minerals that formed. The effects of the presence of phosphate on the rate and extent of Fe(II) production were variable among the Fe(III) oxides, but in general, the highest loadings of phosphate resulted in decreased rates of Fe(II) production, but ultimately higher levels of Fe(II) than in the absence of phosphate. In addition, phosphate concentration had a pronounced effect on the types of secondary minerals that formed; magnetite and chukanovite formed at phosphate concentrations of ≤1 mM (ferrihydrite), <~100 µM (lepidocrocite), 500 µM (feroxyhyte and ferric green rust), while green rust, or green rust and vivianite, formed at phosphate concentrations of 10 mM (ferrihydrite), ≥100 µM (lepidocrocite), and 5 mM (feroxyhyte and ferric green rust). These results further demonstrate that the bioreduction of Fe(III) oxides, and accompanying Fe(II)-bearing secondary mineral formation, is controlled by a complex interplay of mineralogical, geochemical, and microbiological factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Microbial reduction of low-crystallinity tripuhyite (FeSbO 4 ): Implications for Sb(V) cycling in contaminated environments

Tripuhyite (FeSbO 4 ) is an important antimony (Sb)-bearing mineral that controls Sb mobility in contaminated environments, yet its structural stability during microbial reduction remains unresolved. Understanding how FeSbO 4 behaves under anoxic conditions is therefore necessary to predict natural Sb cycling. Here, this study examined how an anaerobic microbial community interacts with FeSbO 4 and alters its structural and redox behavior. Across all conditions, FeSbO 4 released measurable Sb(V), demonstrating that the mineral undergoes partial dissolution in anoxic environment even without microbial activity. However, when extensive microbial Fe(III) reduction occurred in the presence of the electron shuttle anthraquinone-2,6-disulfonate (AQDS), the released Sb was re-immobilized. This indicates that microbial reduction processes modulate Sb mobility. Microbial community analysis showed the enrichment of acetate-utilizing Fe(III)-reducing bacteria as key drivers of Fe reduction. Although secondary Fe minerals were not detected, X-ray absorption fine structure measurements and scanning electron microscopy images revealed the formation of an Sb(III)-bearing phase consistent with valentinite (Sb 2 O 3 ) in the AQDS-amended treatment. This transformation suggests that AQDS not only enhances Fe(III) reduction but is also linked to Sb(V) reduction, and facilitates the immobilization of reduced Sb(III) as Sb 2 O 3 . Overall, this work provides the first evidence that FeSbO 4 is susceptible to microbially mediated redox transformations, and that these processes can significantly alter the mobility and speciation of Sb in reducing environments.

Electron transfer mediator↗
DOE OSTI2024

EPR studies of ferredoxin in spinach and cyanobacterial thylakoids related to photosystem I-driven NADP + reduction

Photosynthetic light-dependent reactions occur in thylakoid membranes where embedded proteins capture light energy and convert it to chemical energy in the form of ATP and NADPH for use in carbon fixation. One of these integral membrane proteins is Photosystem I (PSI). PSI catalyzes light-driven transmembrane electron transfer from plastocyanin (Pc) to oxidized ferredoxin (Fd). Electrons from reduced Fd are used by the enzyme ferredoxin-NADP + reductase (FNR) for the reduction of NADP + to NADPH. Fd and Pc are both small soluble proteins whereas the larger FNR enzyme is associated with the membrane. To investigate electron shuttling between these diffusible and embedded proteins, thylakoid photoreduction of NADP + was studied. As isolated, both spinach and cyanobacterial thylakoids generate NADPH upon illumination without extraneous addition of Fd. These findings indicate that isolated thylakoids either (i) retain a “pool” of Fd which diffuses between PSI and membrane bound FNR or (ii) that a fraction of PSI is associated with Fd, with the membrane environment facilitating PSI-Fd-FNR interactions which enable multiple turnovers of the complex with a single Fd. To explore the functional association of Fd with PSI in thylakoids, electron paramagnetic resonance (EPR) spectroscopic methodologies were developed to distinguish the signals for the reduced Fe-S clusters of PSI and Fd. Temperature-dependent EPR studies show that the EPR signals of the terminal [4Fe-4S] cluster of PSI can be distinguished from the [2Fe-2S] cluster of Fd at > 30 K. At 50 K, the cw X-band EPR spectra of cyanobacterial and spinach thylakoids reduced with dithionite exhibit EPR signals of a [2Fe-2S] cluster with g-values g x = 2.05, g y = 1.96, and g z = 1.89, confirming that Fd is present in thylakoid preparations capable of NADP + photoreduction. Quantitation of the EPR signals of P 700 + and dithionite reduced Fd reveal that Fd is present at a ratio of ~ 1 Fd per PSI monomer in both spinach and cyanobacterial thylakoids. Light-driven electron transfer from PSI to Fd in thylakoids confirms Fd is functionally associated (< 0.4 Fd/PSI) with the acceptor end of PSI in isolated cyanobacterial thylakoids. Furthermore, these EPR experiments provide a benchmark for future spectroscopic characterization of Fd interactions involved in multistep relay of electrons following PSI charge separation in the context of photosynthetic thylakoid microenvironments.

Electron paramagnetic resonance↗
DOE OSTI2025

Expanded Diversity of Microbial Groups Capable of Anaerobic Pyrite Reduction and Assimilation of Dissolution Products

Pyrite, the most abundant iron sulfide mineral in the Earth's crust, has traditionally been considered as a sink for iron and sulfur in the absence of oxygen. Recent research, however, has shown that anaerobic methanogenic archaea can reductively dissolve pyrite and assimilate its products as sources of iron and sulfur. This study explores whether other anaerobic bacteria, including fermentative, nitrate-, iron oxide-, fumarate-, and sulfate-respiring bacteria, can also reduce pyrite and use its dissolution products as sources of iron and sulfur. Results indicate that heterotrophic bacteria respiring fumarate or sulfate, or fermenting organic carbon, can reduce pyrite and assimilate released iron and sulfur. In contrast, nitrate- or iron oxide-respiring cells did not reduce pyrite, suggesting that microbial pyrite reduction is metabolism-specific. All strains capable of reducing pyrite could also use mackinawite as an iron and sulfur source. With the exception of fermentative Bacteroides, strains did not require direct contact with pyrite to reduce the mineral, indicating extracellular electron transfer via electron shuttles. These findings expand the known diversity of microbial groups capable of pyrite reduction and highlight the mineral's lability in various anaerobic environments, with potential implications for the biogeochemical cycles of iron, sulfur, carbon, and oxygen.

58 GEOSCIENCES↗
DOE OSTI2023

Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces

Bio-electrochemical systems (BESs) are promising for renewable energy generation but remain hindered by inefficient electron transfer at electrode surfaces. As the toolbox of bio-anode materials increases, rigorous electrochemical characterization of emerging materials is needed. Here, we holistically characterize the electrochemical interaction of flavin mononucleotide (FMN), an electron shuttle in biological systems and a cofactor for oxidoreductase enzymes, with the bio-inspired mixed conducting polymer poly{3-[6'-(N-methylimidazolium)hexyl]thiophene} (P3HT-Im + ). The behavior of this polymer is compared to the equivalent polymer without the histidine-like imidazolium. We find improved conductivity and charge storage in imidazolium-containing polymers beyond what is explained by differences in the electroactive area. The P3HT-Im + further shows internal charge storage but with negligible faradaic contribution, indicating that charge storage capacity may translate to improved biocatalysis non-intuitive ways. Finally, one-electron transfer is observed between FMN and glassy carbon, while a bio-similar two-electron transfer is observed for the P3HT-Im + . To our knowledge, this is the first example of a concerted two-electron transfer between FMN and an electrode interface, which we attribute to the bio-inspired, histidine-like imidazolium functional groups in the polymer. These studies demonstrate the importance of bio-relevant materials characterization when such materials are deployed in BESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗