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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.

Johnson, M. S.↗
NASA NTRS2012

Adaptation of Organisms by Resonance of RNA Transcription with the Cellular Redox Cycle

Sequence variation in organisms differs across the genome and the majority of mutations are caused by oxidation, yet its origin is not fully understood. It has also been shown that the reduction-oxidation reaction cycle is the fundamental biochemical cycle that coordinates the timing of all biochemical processes in that cell, including energy production, DNA replication, and RNA transcription. It is shown that the temporal resonance of transcriptome biosynthesis with the oscillating binary state of the reduction-oxidation reaction cycle serves as a basis for non-random sequence variation at specific genome-wide coordinates that change faster than by accumulation of chance mutations. This work demonstrates evidence for a universal, persistent and iterative feedback mechanism between the environment and heredity, whereby acquired variation between cell divisions can outweigh inherited variation.

Stolc, Viktor↗
NASA NTRSDate not supplied

Impact of Stress-Activated Positive Holes on the Redox Timing in Organisms Living at the Surface of Rocks: Unlocking Nature's Secrets

Stressing and deforming igneous and/or high-grade metamorphic rocks activates electronic charge carriers known as positive holes, h•, that are defect electrons in the O2–sublattice, e.g. O-states. Like h•in semiconductors, the h•in rocks affect electrical and thermal properties. They produce electrochemical reactions, localized electrical signals, and currents. In this study, we explore the effects of positive holes on the electron flow in the electron transport chain (ETC) of organisms living at the surface of rocks such as gabbro or granite. We found that positive holes, h•, disrupt the in vivotemporal coordination governed by oscillating reduction-oxidation reactions, known as the redox cycle. Positive holes affect the timing of the redox cycle by interacting with essentialmolecules in vivo, leading to the formation of hydroxyl radicals and superoxide anions. We observed that positive holes significantly impede the growth of yeast Saccharomyces cerevisiae(i.e., colony size) and delay the sprouting of broccoli seeds. Additionally, positive holes were found to exert discernible impacts on plant development such as stem length and leaf size. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, shedding light on the potentially significant role of positive holes in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects has implications for a broader understanding of redox biology and of how environmental factors can influence cellular development in natural settings.

hypermutation↗
NASA NTRSDate not supplied

Impact of Stress-Activated Positive Holes on the Redox Timing in Organisms Living at the Surface of Rocks: Unlocking Nature's Secrets

Squeezing and deforming igneous and/or high-grade metamorphic rocks activates electronic charge carriers known as positive holes, h•, that are defect electrons in the O2– sublattice. Similar to h• in semiconductors the h• in rocks affect electrical and thermal properties. They produce electrochemical reactions, localized electrical signals, and currents. In this study, we explore the effects of positive holes on the electron flow in the electron transport chain (ETC) of organisms living at the surface of rocks such as gabbro or granite. We found that positive holes, h•, disrupt the temporal coordination in vivo governed by oscillating reduction-oxidation reactions, known as the redox cycle. Positive holes affect the timing of the redox cycle by interacting with molecules in vivo, leading to the formation of superoxide anions and hydroxyl radicals. Thus, we observed that positive holes significantly impede the growth of yeast Saccharomyces cerevisiae (i.e., colony size) and delay the sprouting of broccoli and chia seeds. Additionally, positive holes were found to exert discernible impacts on plant development such as stem length and leaf size. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, shedding light on the potentially significant role of positive holes in influencing the growth and development of organisms in tectonically stressed rock environments. Understanding these effects has implications for a broader understanding of redox biology and of how environmental factors can influence cellular development in natural settings.

Redox Timing in Organisms↗
NASA NTRS2015

Induction of Oxidation in Living Cells by Time-Varying Electromagnetic Fields

We are studying how biological systems can harness quantum effects of time varying electromagnetic (EM) waves as the time-setting basis for universal biochemical organization via the redox cycle. The effects of extremely weak EM field on the biochemical redox cycle can be monitored through real-time detection of oxidation-induced light emissions of reporter molecules in living cells. It has been shown that EM fields can also induce changes in fluid transport rates through capillaries (approximately 300 microns inner diameter) by generating annular proton gradients. This effect may be relevant to understanding cardiovascular dis-function in spaceflight, beyond the ionosphere. Importantly, we show that these EM effects can be attenuated using an active EM field cancellation device. Central for NASA's Human Research Program is the fact that the absence of ambient EM field in spaceflight can also have a detrimental influence, namely via increased oxidative damage, on DNA replication, which controls heredity.

oxidation↗
NASA NTRS2016

Electromagnetic Basis of Metabolism and Heredity

Living organisms control their cellular biological clocks to maintain functional oscillation of the redox cycle, also called the "metabolic cycle" or "respiratory cycle". Organization of cellular processes requires parallel processing on a synchronized time-base. These clocks coordinate the timing of all biochemical processes in the cell, including energy production, DNA replication, and RNA transcription. When this universal time keeping function is perturbed by exogenous induction of reactive oxygen species (ROS), the rate of metabolism changes. This causes oxidative stress, aging and mutations. Therefore, good temporal coordination of the redox cycle not only actively prevents chemical conflict between the reductive and oxidative partial reactions; it also maintains genome integrity and lifespan. Moreover, this universal biochemical rhythm can be disrupted by ROS induction in vivo. This in turn can be achieved by blocking the electron transport chain either endogenously or exogenously by various metabolites, e.g. hydrogen sulfide (H2S), highly diffusible drugs, and carbon monoxide (CO). Alternatively, the electron transport in vivo can be attenuated via a coherent or interfering transfer of energy from exogenous ultralow frequency (ULF) and extremely low frequency (ELF) electromagnetic (EM) fields, suggesting that-on Earth-such ambient fields are an omnipresent (and probably crucially important) factor for the time-setting basis of universal biochemical reactions in living cells. Our work demonstrated previously un-described evidence for quantum effects in biology by electromagnetic coupling below thermal noise at the universal electron transport chain (ETC) in vivo.

Electromagnetic↗
NASA NTRS1987

Seasonal cycling of sulfur and iron in porewaters of a Delaware salt marsh

An extensive pore water data set has been gathered in the Great Marsh, Delaware over various seasons, salinities, and tides. The data all point to a complimentary redox cycle for sulfur and iron which operates seasonally and tidally. Surface oxidizing conditions prevail in summer, with more reducing conditions at depth during the winter. During the spring tides which flood the marsh, pyrite oxidation occurs releasing excess dissolved iron (II) and sulfate to the porewaters, and precipitating authigenic solid iron phases. The redox conditions in the porewaters of the upper zone during the summer is poised between mildly oxidizing and mildly reducing conditions as shown by pE calculations. This redox environment and intermediate iron-sulfur redox species may be important for the stimulation of plant growth (photosynthesis) and sustenance of a viable microbial community (heterotrophy and chemoautropy).

Luther, George W., III↗
NASA NTRS2016

Oxychlorine Detections on Mars: Implications for Cl Cycling

The Sample Analysis at Mars (SAM) instrument has detected evolved O2 and HCl indicating the presence of perchlorate and/or chlorate (oxychlorine) in all 11 sediments analyzed to date. The hyperarid martian climate is believed to have allowed accumulation of oxychlorine and assumed chloride contents similar to those in hyperarid terrestrial settings. The linear correlation of oxychlorine and chloride of Gale Crater sediments is low (r (sup 2) equals 0.64). Correlations present in hyperarid Antarctica and the Atacama Desert are attributed to unaltered atmospheric source coupled with minimal redox cycling by biological activity. Terrestrial semi-arid to arid settings have low correlations similar to Gale Crater and are attributed to additional inputs of Cl minus from sea salt, dust, and/or proximal playa settings, and possible reduction of oxychlorine phases during wetter periods. While microbiological processes could contribute to low oxychlorine/chloride correlations on Mars, several abiotic mechanisms are more likely, such as changing oxychlorine production rates with time and/or post-depositional geochemical redox processes that altered the Gale Crater oxychlorine and chloride contents.

Sutter, B.↗
NASA NTRSDate not supplied

Stress-Activated Positive Holes (O− in a Matrix of O2–) Cause DNA Damage in Surface-Dwelling Organisms: Unveiling Mutation-Induced Secrets of Nature

Peroxy defects consist of pairs of tightly bonded oxygen anions in the –1 valence state such as in O3X/OO\YO3 with X, Y = Si4+, Al3+ etc. They commonly occur in igneous, metamorphic and many sedimentary rocks. When such rocks are stressed by tectonic forces, peroxy defects break up, releasing highly mobile electronic charge carriers: defect electrons in the O2– sublattice, i.e. unbound O–, known as “positive holes”, h•. The h• can flow out of stressed rock volumes, spreading far and wide, causing electric currents and electrochemical reactions. This study explores how the h• impact the electron flow in the electron transport chain (ETC) of organisms on the surface of rocks such as gabbro and granite. We found that, by forming hydroxyl radicals and superoxide anions, the h• disrupt the in vivo coordination of reduction-oxidation reactions that are essential for the timing of the redox cycle. Our observations show that stress activation of h• delays the sprouting of certain plant seeds and impedes the growth of yeast cultures, Saccharomyces cerevisiae. The h• induce mutations and affect plant development as evidenced by reduced stem length and leaf size. At the same time, the h• serve as a source of abiotic oxidation, capable of forming various organic compounds in situ. Through the generation of radical species that create new carbon-carbon bonds the h• facilitate the abiotic synthesis of hydrocarbons and other organic molecules essential to life, including porphyrins. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, revealing their significant role in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects enhances our broader comprehension of redox biology and the influence of environmental factors on cellular development in natural settings.

astrobiology↗
NASA NTRS1981

Requirements for optimization of electrodes and electrolyte for the iron/chromium Redox flow cell

Improved catalyzation techniques that included a pretreatment of carbon substrate and provided normalized carbon surface for uniform gold deposition were developed. This permits efficient use of different batches of carbon felt materials which initially vary significantly in their physical and surface chemical properties, as well as their electrochemical behavior. Further modification of gold impregnation technique gave the best performing electrodes. In addition to the linear sweep voltammetry, cyclic voltammetry was used to determine the effects of different activation procedures on the Cr(3)/Cr(2) Redox and H2 evolution reactions. The roles of carbon, gold and lead in the overall Redox cycle are identified. The behavior of the electrodes at both normal battery operating potentials and more extreme potentials is discussed preparing efficient and stable electrodes for the energy storage battery is implicated.

Jalan, V.↗
NASA NTRS1992

The role of certain infauna and vascular plants in the mediation of redox reactions in marine sediments

The mechanisms by which certain animals and plants affect redox processes in sediments was examined by studying three environments: (1) subtidal sediments dominated by the deposit-feeding polychaete Heteromastus filiformis; (2) a saltmarsh inhabited by the tall form of Spartina alterniflora; and (3) tropical carbonate sediments inhabited by three species of seagrasses. S-35-sulfide production rates were compared to pool sizes of dissolved sulfide and dissolved iron. In all of the sediments studied, rates of sulfide reduction were enhanced by macroorganisms while the rate of turnover of dissolved sulfide increased. The polychaete enhanced microbial activity and redox cycling primarily by subducting particles of organic matter and oxidized iron during sediment reworking. The Spartina species enhanced anaerobic activity by transporting primarily dissolved organic matter and oxidants. Although the final result of both animal and plant activities was the enhancement of sub-surface cycling of sulfur and iron, decreased dissolved sulfide and increased dissolved iron concentrations, the mechanisms which produced these results differed dramatically.

Hines, Mark E.↗
NASA NTRS2002

Activation of c-Jun N-terminal kinase and apoptosis in endothelial cells mediated by endogenous generation of hydrogen peroxide

Reactive oxygen species have been implicated in the activation of signal transduction pathways. However, extracellular addition of oxidants such as hydrogen peroxide (H2O2) often requires concentrations that cannot be readily achieved under physiological conditions to activate biological responses such as apoptosis. Explanations for this discrepancy have included increased metabolism of H2O2 in the extracellular environment and compartmentalization within the cell. We have addressed this issue experimentally by examining the induction of apoptosis of endothelial cells induced by exogenous addition of H2O2 and by a redox cycling agent, 2,3-dimethoxy-1,4-naphthoquinone, that generates H2O2 in cells. Here we show that low nanomolar steady-state concentrations (0.1-0.5 nmol x min(-1) x 10(6) cells) of H2O2 generated intracellularly activate c-Jun N terminal kinase and initiate apoptosis in endothelial cells. A comparison with bolus hydrogen peroxide suggests that the low rate of intracellular formation of this reactive oxygen species results in a similar profile of activation for both c-Jun N terminal kinase and the initiation of apoptosis. However, a detailed analysis reveals important differences in both the duration and profile for activation of these signaling pathways.

Non-NASA Center↗
NASA NTRS1998

Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

NASA Discipline Regulatory Physiology↗
NASA NTRS2010

Novel Thermotolerant Siderophilic Filamentous Cyanobacterium that Produces Intracellular Iron-Rich Phases

Cyanobacteria are the main producers of organic compounds in iron-depositing hot springs despite photosynthetically generated-oxygen and the abundance of reduced iron (Fe2+) that likely leads to enormous oxidative stress within cyanobacterial cells. Therefore, the study of cyanobacterial diversity, phylogeny, and biogeochemical activity in iron-depositing hot springs will not only provide insights into the contribution of CB to iron redox cycling in these environments, but it could also provide insights into CB evolution. This study characterizes the phylogeny, morphology, and physiology of isolate JSC-1, a novel filamentous CB isolated from an iron-depositing hot spring. While isolate JSC-1 is morphologically similar to the CB genus Leptolyngbya, 16S rDNA sequence data indicated that it shares 95 percent sequence similarity to the type strain L. boryanum. Strain JSC-1 fixes N2 and exhibited an unusually high ratio between photosystem (PS) I and PS II and was capable of complementary chromatic adaptation. Further, it synthesized only chlorophyll a and a unique set of carotenoids. Strain JSC-1 not only required high levels of Fe for growth (greater than or equal to 40 microM), but it also accumulated large amounts of extracellular ferrihydrite and generated intracellular ferric phosphates. Strain JSC-1 was found to secrete 2-oxoglutaric acid and possesses one ortholog and one paralog of bacterioferritin. Surprisingly, the latter has 70.13 % identity with a bacterioferritin in marine-proteobacterium HTCC 2080 and has joint node with bacterioferritins found in enterobacteria. Collectively, these observations provide insights into the physiological strategies that might have allowed CB to develop and proliferate in Fe-rich environments. Based on its genotypic and phenotypic characterization of strain, JSC-1 represents a new operational taxonomical unit (OTU) JSC-1.

Broun, Igor I.↗
NASA NTRS1985

Cycling Performance of the Iron-Chromium Redox Energy Storage System

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗
NASA NTRS1985

Cycling performance of the iron-chromium redox energy storage system

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗