Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water.

PubMed

Sit, Patrick H-L; Car, Roberto; Cohen, Morrel H; Selloni, Annabella

2013-02-05

Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 10(4)/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe](P)/FeS(2), a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe](P)/FeS(2) is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.

Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water

PubMed Central

Sit, Patrick H.-L.; Car, Roberto; Cohen, Morrel H.; Selloni, Annabella

2013-01-01

Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 104/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe]P/FeS2, a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe]P/FeS2 is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant. PMID:23341607

Evolution from S3 to S4 States of the Oxygen-Evolving Complex in Photosystem II Monitored by Quantum Mechanics/Molecular Mechanics (QM/MM) Dynamics.

PubMed

Narzi, Daniele; Capone, Matteo; Bovi, Daniele; Guidoni, Leonardo

2018-04-16

Water oxidation in the early steps of natural photosynthesis is fulfilled by photosystem II, which is a protein complex embedded in the thylakoid membrane inside chloroplasts. The water oxidation reaction occurs in the catalytic core of photosystem II, which consists of a Mn4Ca metal cluster, at which, after the accumulation of four oxidising equivalents through five steps (S0-S4) of the Kok-Joliot cycle, two water molecules are split into electrons, protons, and molecular oxygen. In recent years, by combining experimental and theoretical approaches, new insights have been achieved into the structural and electronic properties of different steps of the catalytic cycle. Nevertheless, the exact catalytic mechanism, especially concerning the final stages of the cycle, remains elusive and greatly debated. Herein, by means of quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations, from the structural, electronic, and magnetic points of view, the S 3 state before and upon oxidation has been characterised. In contrast with the S 2 state, the oxidation of the S 3 state is not followed by a spontaneous proton-coupled electron-transfer event. Nevertheless, upon modelling the reduction of the tyrosine residue in photosystem II (Tyr Z ) and the protonation of Asp61, spontaneous proton transfer occurs, leading to the deprotonation of an oxygen atom bound to Mn1; thus making it available for O-O bond formation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

PubMed

Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

2016-04-28

The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation.

First-charge instabilities of layered-layered lithium-ion-battery materials.

PubMed

Croy, Jason R; Iddir, Hakim; Gallagher, Kevin; Johnson, Christopher S; Benedek, Roy; Balasubramanian, Mahalingam

2015-10-07

Li- and Mn-rich layered oxides with composition xLi2MnO3·(1 -x)LiMO2 enable high capacity and energy density Li-ion batteries, but suffer from degradation with cycling. Evidence of atomic instabilities during the first charge are addressed in this work with X-ray absorption spectroscopy, first principles simulation at the GGA+U level, and existing literature. The pristine material of composition xLi2MnO3·(1 -x)LiMn0.5Ni0.5O2 is assumed in the simulations to have the form of LiMn2 stripes, alternating with NiMn stripes, in the metal layers. The charged state is simulated by removing Li from the Li layer, relaxing the resultant system by steepest descents, then allowing the structure to evolve by molecular dynamics at 1000 K, and finally relaxing the evolved system by steepest descents. The simulations show that about ¼ of the oxygen ions in the Li2MnO3 domains are displaced from their original lattice sites, and form oxygen-oxygen bonds, which significantly lowers the energy, relative to that of the starting structure in which the oxygen sublattice is intact. An important consequence of the displacement of the oxygen is that it enables about ⅓ of the (Li2MnO3 domain) Mn ions to migrate to the delithiated Li layers. The decrease in the coordination of the Mn ions is about twice that of the Ni ions. The approximate agreement of simulated coordination number deficits for Mn and Ni following the first charge with analysis of EXAFS measurements on 0.3Li2MnO3·0.7LiMn0.5Ni0.5O2 suggests that the simulation captures significant features of the real material.

Effects of oxygen partial pressure on Li-air battery performance

NASA Astrophysics Data System (ADS)

Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

2017-10-01

For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

Properties of evolved mass-losing stars in the Milky Way and variations in the interstellar dust composition

NASA Technical Reports Server (NTRS)

Thronson, Harley A., Jr.; Latter, William B.; Black, John H.; Bally, John; Hacking, Perry

1987-01-01

A large sample of evolved carbon-rich and oxygen-rich objects has been studied using data from the IRAS Point Source Catalog. The number density of infrared-emitting 'carbon' stars shows no variation with Galactocentric radius, while the evolved 'oxygen' star volume density can be well fitted by a given law. A law is given for the number of carbon stars; a total is found in the Galaxy of 48,000 highly evolved oxygen stars. The mass-return rate for all evolved stars is found to be 0.35 solar mass/yr, with a small percentage contribution from carbon stars. The mass-loss rates for both types of stars are dominated by the small number of objects with the smallest rates. A mean lifetime of about 200,000 yr is obtained for both carbon and oxygen stars. Main-sequence stars in the mass range of three to five solar masses are the probable precursors of the carbon stars.

Goldilocks and the three inorganic equilibria: how Earth's chemistry and life coevolve to be nearly in tune.

PubMed

Rickaby, R E M

2015-03-13

Life and the chemical environment are united in an inescapable feedback cycle. The periodic table of the elements essential for life has transformed over Earth's history, but, as today, evolved in tune with the elements available in abundance in the environment. The most revolutionary time in life's history was the advent and proliferation of oxygenic photosynthesis which forced the environment towards a greater degree of oxidation. Consideration of three inorganic chemical equilibria throughout this gradual oxygenation prescribes a phased release of trace metals to the environment, which appear to have coevolved with employment of these new chemicals by life. Evolution towards complexity was chemically constrained, and changes in availability of notably Fe, Zn and Cu paced the systematic development of complex organisms. Evolving life repeatedly catalysed its own chemical challenges via the unwitting release of new and initially toxic chemicals. Ultimately, the harnessing of these allowed life to advance to greater complexity, though the mechanism responsible for translating novel chemistry to heritable use remains elusive. Whether a chemical acts as a poison or a nutrient lies both in the dose and in its environmental history. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

What spectroscopy reveals concerning the Mn oxidation levels in the oxygen evolving complex of photosystem II: X-ray to near infra-red.

PubMed

Pace, Ron J; Jin, Lu; Stranger, Rob

2012-08-28

Photosystem II (PS II), found in oxygenic photosynthetic organisms, catalyses the most energetically demanding reaction in nature, the oxidation of water to molecular oxygen and protons. The water oxidase in PS II contains a Mn(4)Ca cluster (oxygen evolving complex, OEC), whose catalytic mechanism has been extensively investigated but is still unresolved. In particular the precise Mn oxidation levels through which the cluster cycles during functional turnover are still contentious. In this, the first of several planned parts, we examine a broad range of published data relating to this question, while considering the recent atomic resolution PS II crystal structure of Umena et al. (Nature, 2011, 473, 55). Results from X-ray, UV-Vis and NIR spectroscopies are considered, using an approach that is mainly empirical, by comparison with published data from known model systems, but with some reliance on computational or other theoretical considerations. The intention is to survey the extent to which these data yield a consistent picture of the Mn oxidation states in functional PS II - in particular, to test their consistency with two current proposals for the mean redox levels of the OEC during turnover; the so called 'high' and 'low' oxidation state paradigms. These systematically differ by two oxidation equivalents throughout the redox accumulating catalytic S state cycle (states S(0)···S(3)). In summary, we find that the data, in total, substantially favor the low oxidation proposal, particularly as a result of the new analyses we present. The low oxidation state scheme is able to resolve a number of previously 'anomalous' results in the observed UV-Visible S state turnover spectral differences and in the resonant inelastic X-ray spectroscopy (RIXS) of the Mn pre-edge region of the S(1) and S(2) states. Further, the low oxidation paradigm is able to provide a 'natural' explanation for the known sensitivity of the OEC Mn cluster to cryogenic near infra-red (NIR) induced turnover to alternative spin/redox states in S(2) and S(3).

Bacterial sulfur disproportionation constrains timing of neoproterozoic oxygenation

USGS Publications Warehouse

Kunzmann, Marcus; Bui, Thi Hao; Crockford, Peter W.; Halverson, Galen P.; Scott, Clinton T.; Lyons, Timothy W.; Wing, Boswell A.

2017-01-01

Various geochemical records suggest that atmospheric O2 increased in the Ediacaran (635–541 Ma), broadly coincident with the emergence and diversification of large animals and increasing marine ecosystem complexity. Furthermore, geochemical proxies indicate that seawater sulfate levels rose at this time too, which has been hypothesized to reflect increased sulfide oxidation in marine sediments caused by sediment mixing of the newly evolved macrofauna. However, the exact timing of oxygenation is not yet understood, and there are claims for significant oxygenation prior to the Ediacaran. Furthermore, recent evidence suggests that physical mixing of sediments did not become important until the late Silurian. Here we report a multiple sulfur isotope record from a ca. 835–630 Ma succession from Svalbard, further supported by data from Proterozoic strata in Canada, Australia, Russia, and the United States, in order to investigate the timing of oxygenation. We present isotopic evidence for onset of globally significant bacterial sulfur disproportionation and reoxidative sulfur cycling following the 635 Ma Marinoan glaciation. Widespread sulfide oxidation helps to explain the observed first-order increase in seawater sulfate concentration from the earliest Ediacaran to the Precambrian-Cambrian boundary by reducing the amount of sulfur buried as pyrite. Expansion of reoxidative sulfur cycling to a global scale also indicates increasing environmental O2 levels. Thus, our data suggest that increasing atmospheric O2 levels may have played a role in the emergence of the Ediacaran macrofauna and increasing marine ecosystem complexity.

Earth's oxygen cycle and the evolution of animal life.

PubMed

Reinhard, Christopher T; Planavsky, Noah J; Olson, Stephanie L; Lyons, Timothy W; Erwin, Douglas H

2016-08-09

The emergence and expansion of complex eukaryotic life on Earth is linked at a basic level to the secular evolution of surface oxygen levels. However, the role that planetary redox evolution has played in controlling the timing of metazoan (animal) emergence and diversification, if any, has been intensely debated. Discussion has gravitated toward threshold levels of environmental free oxygen (O2) necessary for early evolving animals to survive under controlled conditions. However, defining such thresholds in practice is not straightforward, and environmental O2 levels can potentially constrain animal life in ways distinct from threshold O2 tolerance. Herein, we quantitatively explore one aspect of the evolutionary coupling between animal life and Earth's oxygen cycle-the influence of spatial and temporal variability in surface ocean O2 levels on the ecology of early metazoan organisms. Through the application of a series of quantitative biogeochemical models, we find that large spatiotemporal variations in surface ocean O2 levels and pervasive benthic anoxia are expected in a world with much lower atmospheric pO2 than at present, resulting in severe ecological constraints and a challenging evolutionary landscape for early metazoan life. We argue that these effects, when considered in the light of synergistic interactions with other environmental parameters and variable O2 demand throughout an organism's life history, would have resulted in long-term evolutionary and ecological inhibition of animal life on Earth for much of Middle Proterozoic time (∼1.8-0.8 billion years ago).

'water splitting' by titanium exchanged zeolite A. Technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuznicki, S.M.; Eyring, E.M.

1978-09-01

Visually detectable and chromatographically and mass spectrally identified hydrogen gas evolves from titanium (III) exchanged zeolite A immersed in water and illuminated with visible light. Titanium(III) exchanged zeolite X and zeolite Y do not produce this reaction. A photochemically produced, oxygenated titanium free radical (detected by electron spin resonance) not previously described is the species in the zeolite that reduces protons to molecular hydrogen. The other product of this reduction step is a nonradical, oxygenated titanium species of probable empirical formula TiO4. Heating the spent oxygenated titanium containing zeolite A under vacuum at 375 C restores over fifty percent ofmore » the free radical. Unlike previously reported systems, heating does not restore the original aquotitanium(III) species in the zeolite. Thus a means other than heating must be found to achieve a closed photochemical cycle that harnesses visible solar energy in the production of molecular hydrogen. The titanium exchanged zeolite A does, however, lend itself to a thermolysis of water previously described by Kasai and Bishop. (Author)« less

Reversal of Increasing Tropical Ocean Hypoxia Trends With Sustained Climate Warming

NASA Astrophysics Data System (ADS)

Fu, Weiwei; Primeau, Francois; Keith Moore, J.; Lindsay, Keith; Randerson, James T.

2018-04-01

Dissolved oxygen (O2) is essential for the survival of marine animals. Climate change impacts on future oxygen distributions could modify species biogeography, trophic interactions, biodiversity, and biogeochemistry. The Coupled Model Intercomparison Project Phase 5 models predict a decreasing trend in marine O2 over the 21st century. Here we show that this increasing hypoxia trend reverses in the tropics after 2100 in the Community Earth System Model forced by atmospheric CO2 from the Representative Concentration Pathway 8.5 and Extended Concentration Pathway 8.5. In tropical intermediate waters between 200 and 1,000 m, the model predicts a steady decline of O2 and an expansion of oxygen minimum zones (OMZs) during the 21st century. By 2150, however, the trend reverses with oxygen concentration increasing and OMZ volume shrinking through 2300. A novel five-box model approach in conjunction with output from the full Earth system model is used to separate the contributions of biological and physical processes to the trends in tropical oxygen. The tropical O2 recovery is caused mainly by reductions in tropical biological export, coupled with a modest increase in ventilation after 2200. The time-evolving oxygen distribution impacts marine nitrogen cycling, with potentially important climate feedbacks.

Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex

ERIC Educational Resources Information Center

Howard, Derrick L.; Tinoco, Arthur D.; Brudvig, Gary W.; Vrettos, John S.; Allen, Bertha Connie

2005-01-01

Bioinorganic models of the manganese Mn4 cluster are important not only as aids in understanding the structure and function of the oxygen-evolving complex (OEC), but also in developing artificial water-oxidation catalysts. The mechanism of water oxidation by photosystem II (PSII) is thought to involve the formation of a high-valent terminal Mn-oxo…

Balance of oxygen throughout the conversion of a high-level waste melter feed to glass

DOE PAGES

Lee, SeungMin; Hrma, Pavel; Kloužek, Jaroslav; ...

2017-07-03

Gases evolve from nuclear waste melter feed during conversion to glass in response to heating. This article is focused on oxygen mass balance based on the stoichiometry of feed melting reactions and evolved-gas analysis data. Whereas O 2-producing and -consuming batch-melting reactions are complete in the reacting and primary-foam layers of the cold cap, O 2 from redox reactions continues to evolve as long as melt temperature increases, and thus generates secondary foam. Also, we discuss the relationship between the oxygen mass balance and the temperature-dependent iron redox ratio and the O 2 partial pressure, as they evolve during themore » feed-to-glass conversion.« less

Balance of oxygen throughout the conversion of a high-level waste melter feed to glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, SeungMin; Hrma, Pavel; Kloužek, Jaroslav

Gases evolve from nuclear waste melter feed during conversion to glass in response to heating. This article is focused on oxygen mass balance based on the stoichiometry of feed melting reactions and evolved-gas analysis data. Whereas O 2-producing and -consuming batch-melting reactions are complete in the reacting and primary-foam layers of the cold cap, O 2 from redox reactions continues to evolve as long as melt temperature increases, and thus generates secondary foam. Also, we discuss the relationship between the oxygen mass balance and the temperature-dependent iron redox ratio and the O 2 partial pressure, as they evolve during themore » feed-to-glass conversion.« less

Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruther, Rose E.; Samuthira Pandian, Amaresh; Yan, Pengfei

2017-03-21

Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD,more » TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

Nitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Dhavale, Vishal M.; Gaikwad, Sachin S.; George, Leena; Devi, R. Nandini; Kurungot, Sreekumar

2014-10-01

Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well.Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well. Electronic supplementary information (ESI) available: An experimental procedure for the synthesis of GO, Gr, Ni-particles, and Ni-Gr. TEM images of Gr, NGr, and Ni-Gr. XPS of C 1s and O 1s of Ni-NGr. C 1s, O 1s and N 1s spectra of NGr. A comparative cyclic voltammogram of NGr and Ni-NGr. A Tafel plot, RRDE, HR-TEM image of Ni-NGr and the corresponding line profile showing the lattice spacing values, anodic scan of NGr. Comparative anodic scan of Ni-particles, Ni-Gr and Ni-NGr. CV of the Pt-electrode and capacitive CV. SEM elemental mapping and the mechanism of OER. See DOI: 10.1039/c4nr03578j

Planktonic Marine Iron-Oxidizers Drive Iron(III) Mineralization Under Low Oxygen Conditions

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Field, E.; Findlay, A.; MacDonald, D. J.; Chan, C. S. Y.; Kato, S.

2016-02-01

Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive banded iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypotheses was that cyanobacteria produced oxygen that oxidized iron(II) abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron(II)-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron-oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to iron deposits, but there is currently little evidence for planktonic marine iron-oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron-oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 µM O2, <0.2 µM H2S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Instead, cyanobacteria may be providing oxygen for microaerophilic iron(II) oxidation through a symbiotic relationship that promotes oxygen consumption rather than build-up. Our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron(II)-oxidizers were likely important drivers of iron(III) mineralization in ancient oceans.

Contribution of Proton Capture Reactions to the Ascertained Abundance of Fluorine in the Evolved Stars of Globular Cluster M4, M22, 47 Tuc and NGC 6397

NASA Astrophysics Data System (ADS)

Mahanta, Upakul; Goswami, Aruna; Duorah, H. L.; Duorah, K.

2017-12-01

The origin of the abundance pattern and also the (anti)correlation present among the elements found in stars of globular clusters (GCs) remains unimproved until date. The proton-capture reactions are presently recognised in concert of the necessary candidates for that sort of observed behaviour in the second generation stars. We tend to propose a reaction network of a nuclear cycle namely carbon-nitrogen-oxygen-fluorine (CNOF) at evolved stellar condition since fluorine (^{19}F) is one such element which gets plagued by proton capture reactions. The stellar temperature thought about here ranges from 2× 107 to 10× 107 K and there has been an accretion occuring, with material density being 102 g/cm3 and 103 g/cm3. Such kind of temperature density conditions are probably going to be prevailing within the H-burning shell of evolved stars. The estimated abundances of ^{19}F are then matched with the info that has been determined for a few some metal-poor giants of GC M4, M22, 47 Tuc as well as NGC 6397. As far as the comparison between the observed and calculated abundances is concerned, it is found that the abundance of ^{19}F have shown an excellent agreement with the observed abundances with a correlation coefficent above 0.9, supporting the incidence of that nuclear cycle at the adopted temperature density conditions.

The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data.

PubMed

Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S

2017-01-17

Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn 4 O 5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage "S" states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves through the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O 2 evolution. The structure of the dark-stable S 1 state has been a target for X-ray crystallography for the past 15 years. However, traditional X-ray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S 1 state. However, the atom positions in this crystal structure are still not consistent with high-resolution EXAFS spectroscopy, partially due to the poorly resolved oxygen positions next to Mn centers and partial reduction due to extended dark adaptation of the sample. These inconsistencies led to the new models of the OEC with an alternative low oxidation state and raised questions on the protonation state of the cluster, especially the O5 μ-oxo bridge. This Account summarizes the most recent models of the OEC that emerged from QM/MM, EXAFS and femtosecond X-ray crystallography methods. When PSII in the S 1 state is exposed to light, the S 1 state is advanced to the higher oxidation states and eventually binds substrate water molecules. Identifying the substrate waters is of paramount importance for establishing the water-oxidation mechanism but is complicated by a large number of spectroscopically similar waters. Water analogues can, therefore, be helpful because they serve as spectroscopic markers that help to track the motion of the substrate waters. Due to a close structural and electronic similarity to water, ammonia has been of particular interest. We review three competing hypotheses on substrate water/ammonia binding and compile theoretical and experimental evidence to support them. Binding of ammonia as a sixth ligand to Mn4 during the S 1 → S 2 transition seems to satisfy most of the criteria, especially the most compelling recent EPR data on D1-D61A mutated PSII. Such a binding mode suggests delivery of water from the "narrow" channel through a "carousel" rearrangement of waters around Mn4 upon the S 2 → S 3 transition. An alternative hypothesis suggests water delivery through the "large" channel on the Ca side. However, both water delivery paths lead to a similar S 3 structure, seemingly reaching consensus on the nature of the last detectable S-state intermediate in the Kok cycle before O 2 evolution.

The O 2 -Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data

DOE PAGES

Askerka, Mikhail; Brudvig, Gary W.; Batista, Victor S.

2016-12-21

Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn 4O 5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage “S” states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves throughmore » the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/ MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O 2 evolution. The structure of the dark-stable S1 state has been a target for X-ray crystallography for the past 15 years. However, traditional Xray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S 1 state. However, the atom positions in this crystal structure are still not consistent with high-resolution EXAFS spectroscopy, partially due to the poorly resolved oxygen positions next to Mn centers and partial reduction due to extended dark adaptation of the sample. These inconsistencies led to the new models of the OEC with an alternative low oxidation state and raised questions on the protonation state of the cluster, especially the O5 μ-oxo bridge. This Account summarizes the most recent models of the OEC that emerged from QM/MM, EXAFS and femtosecond X-ray crystallography methods. When PSII in the S 1 state is exposed to light, the S 1 state is advanced to the higher oxidation states and eventually binds substrate water molecules. Identifying the substrate waters is of paramount importance for establishing the water-oxidation mechanism but is complicated by a large number of spectroscopically similar waters. Water analogues can, therefore, be helpful because they serve as spectroscopic markers that help to track the motion of the substrate waters. Due to a close structural and electronic similarity to water, ammonia has been of particular interest. We review three competing hypotheses on substrate water/ammonia binding and compile theoretical and experimental evidence to support them. Binding of ammonia as a sixth ligand to Mn4 during the S 1 → S 2 transition seems to satisfy most of the criteria, especially the most compelling recent EPR data on D1-D61A mutated PSII. Such a binding mode suggests delivery of water from the “narrow” channel through a “carousel” rearrangement of waters around Mn4 upon the S 2 → S 3 transition. An alternative hypothesis suggests water delivery through the “large” channel on the Ca side. However, both water delivery paths lead to a similar S 3 structure, seemingly reaching consensus on the nature of the last detectable S-state intermediate in the Kok cycle before O 2 evolution.« less

The O 2 -Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Askerka, Mikhail; Brudvig, Gary W.; Batista, Victor S.

Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn 4O 5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage “S” states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves throughmore » the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/ MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O 2 evolution. The structure of the dark-stable S1 state has been a target for X-ray crystallography for the past 15 years. However, traditional Xray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S 1 state. However, the atom positions in this crystal structure are still not consistent with high-resolution EXAFS spectroscopy, partially due to the poorly resolved oxygen positions next to Mn centers and partial reduction due to extended dark adaptation of the sample. These inconsistencies led to the new models of the OEC with an alternative low oxidation state and raised questions on the protonation state of the cluster, especially the O5 μ-oxo bridge. This Account summarizes the most recent models of the OEC that emerged from QM/MM, EXAFS and femtosecond X-ray crystallography methods. When PSII in the S 1 state is exposed to light, the S 1 state is advanced to the higher oxidation states and eventually binds substrate water molecules. Identifying the substrate waters is of paramount importance for establishing the water-oxidation mechanism but is complicated by a large number of spectroscopically similar waters. Water analogues can, therefore, be helpful because they serve as spectroscopic markers that help to track the motion of the substrate waters. Due to a close structural and electronic similarity to water, ammonia has been of particular interest. We review three competing hypotheses on substrate water/ammonia binding and compile theoretical and experimental evidence to support them. Binding of ammonia as a sixth ligand to Mn4 during the S 1 → S 2 transition seems to satisfy most of the criteria, especially the most compelling recent EPR data on D1-D61A mutated PSII. Such a binding mode suggests delivery of water from the “narrow” channel through a “carousel” rearrangement of waters around Mn4 upon the S 2 → S 3 transition. An alternative hypothesis suggests water delivery through the “large” channel on the Ca side. However, both water delivery paths lead to a similar S 3 structure, seemingly reaching consensus on the nature of the last detectable S-state intermediate in the Kok cycle before O 2 evolution.« less

An intrinsically disordered photosystem II subunit, PsbO, provides a structural template and a sensor of the hydrogen-bonding network in photosynthetic water oxidation.

PubMed

Offenbacher, Adam R; Polander, Brandon C; Barry, Bridgette A

2013-10-04

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global (13)C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster.

Solar High Temperature Water-Splitting Cycle with Quantum Boost

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, Robin; Davenport, Roger; Talbot, Jan

A sulfur family chemical cycle having ammonia as the working fluid and reagent was developed as a cost-effective and efficient hydrogen production technology based on a solar thermochemical water-splitting cycle. The sulfur ammonia (SA) cycle is a renewable and sustainable process that is unique in that it is an all-fluid cycle (i.e., with no solids handling). It uses a moderate temperature solar plant with the solar receiver operating at 800°C. All electricity needed is generated internally from recovered heat. The plant would operate continuously with low cost storage and it is a good potential solar thermochemical hydrogen production cycle formore » reaching the DOE cost goals. Two approaches were considered for the hydrogen production step of the SA cycle: (1) photocatalytic, and (2) electrolytic oxidation of ammonium sulfite to ammonium sulfate in aqueous solutions. Also, two sub-cycles were evaluated for the oxygen evolution side of the SA cycle: (1) zinc sulfate/zinc oxide, and (2) potassium sulfate/potassium pyrosulfate. The laboratory testing and optimization of all the process steps for each version of the SA cycle were proven in the laboratory or have been fully demonstrated by others, but further optimization is still possible and needed. The solar configuration evolved to a 50 MW(thermal) central receiver system with a North heliostat field, a cavity receiver, and NaCl molten salt storage to allow continuous operation. The H2A economic model was used to optimize and trade-off SA cycle configurations. Parametric studies of chemical plant performance have indicated process efficiencies of ~20%. Although the current process efficiency is technically acceptable, an increased efficiency is needed if the DOE cost targets are to be reached. There are two interrelated areas in which there is the potential for significant efficiency improvements: electrolysis cell voltage and excessive water vaporization. Methods to significantly reduce water evaporation are proposed for future activities. Electrolysis membranes that permit higher temperatures and lower voltages are attainable. The oxygen half cycle will need further development and improvement.« less

System Evaluation and Economic Analysis of a HTGR Powered High-Temperature Electrolysis Hydrogen Production Plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael G. McKellar; Edwin A. Harvego; Anastasia A. Gandrik

2010-10-01

A design for a commercial-scale high-temperature electrolysis (HTE) plant for hydrogen production has been developed. The HTE plant is powered by a high-temperature gas-cooled reactor (HTGR) whose configuration and operating conditions are based on the latest design parameters planned for the Next Generation Nuclear Plant (NGNP). The current HTGR reference design specifies a reactor power of 600 MWt, with a primary system pressure of 7.0 MPa, and reactor inlet and outlet fluid temperatures of 322°C and 750°C, respectively. The power conversion unit will be a Rankine steam cycle with a power conversion efficiency of 40%. The reference hydrogen production plantmore » operates at a system pressure of 5.0 MPa, and utilizes a steam-sweep system to remove the excess oxygen that is evolved on the anode (oxygen) side of the electrolyzer. The overall system thermal-to-hydrogen production efficiency (based on the higher heating value of the produced hydrogen) is 40.4% at a hydrogen production rate of 1.75 kg/s and an oxygen production rate of 13.8 kg/s. An economic analysis of this plant was performed with realistic financial and cost estimating assumptions. The results of the economic analysis demonstrated that the HTE hydrogen production plant driven by a high-temperature helium-cooled nuclear power plant can deliver hydrogen at a cost of $3.67/kg of hydrogen assuming an internal rate of return, IRR, of 12% and a debt to equity ratio of 80%/20%. A second analysis shows that if the power cycle efficiency increases to 44.4%, the hydrogen production efficiency increases to 42.8% and the hydrogen and oxygen production rates are 1.85 kg/s and 14.6 kg/s respectively. At the higher power cycle efficiency and an IRR of 12% the cost of hydrogen production is $3.50/kg.« less

Artificial synthetic Mn(IV)Ca-oxido complexes mimic the oxygen-evolving complex in photosystem II.

PubMed

Chen, Changhui; Zhang, Chunxi; Dong, Hongxing; Zhao, Jingquan

2015-03-14

A novel family of heteronuclear Mn(IV)Ca-oxido complexes containing Mn(IV)Ca-oxido cuboidal moieties and reactive water molecules on Ca(2+) have been synthesized and characterized to mimic the oxygen-evolving complex (OEC) of photosystem II (PSII) in nature.

Sage Studies Of The Mass Return From AGB And RSG Stars In The Large Magellanic Cloud

NASA Astrophysics Data System (ADS)

Sargent, Benjamin A.; Srinivasan, S.; Meixner, M.

2011-01-01

The Surveying the Agents of a Galaxy's Evolution (SAGE; PI: M. Meixner) Spitzer Space Telescope Legacy project aims to further our understanding of the life cycle of matter in galaxies by studying this life cycle in our neighboring galaxy, the Large Magellanic Cloud (LMC). Combining SAGE mid-infrared photometry with that at shorter wavelengths from other catalogs, the spectral energy distribution (SED) for each of >25000 Asymptotic Giant Branch (AGB) and Red Supergiant (RSG) stars in the LMC has been assembled. To model mass loss from these stars, my colleagues and I have constructed the grid of RSG and AGB models (GRAMS) using the radiative transfer code 2Dust. I will discuss how GRAMS was constructed, and how we use it to determine the mass-loss rate for each evolved star studied, which gives the total mass-loss return to the LMC from AGB and RSG stars. In my talk, I show how this total mass-loss return is divided into oxygen-rich (O-rich) and carbon-rich (C-rich) dust using SED-fitting to identify O-rich versus C-rich AGB stars. Applications of this work to determining the mass return from evolved stars in other galaxies, including the Milky Way, will also be discussed.

Plate tectonics, habitability and life

NASA Astrophysics Data System (ADS)

Spohn, Tilman; Breuer, Doris

2016-04-01

The role of plate tectonics in defining habitability of terrestrial planets is being increasingly discussed (e.g., Elkins-Tanton, 2015). Plate tectonics is a significantly evolved concept with a large variety of aspects. In the present context, cycling of material between near surface and mantle reservoirs is most important. But increased heat transport through mixing of cold lithosphere with the deep interior and formation of continental crust may also matter. An alternative mechanism of material cycling between these reservoirs is hot-spot volcanism combined with crust delamination. Hot-spot volcanism will transport volatiles to the atmosphere while delamination will mix crust, possibly altered by sedimentation and chemical reactions, with the mantle. The mechanism works as long as the stagnant lithosphere plate has not grown thicker than the crust and as long as volcanic material is added onto the crust. Thermal evolution studies suggest that the mechanism could work for the first 1-2 Ga of planetary evolution. The efficiency of the mechanism is limited by the ratio of extrusive to intrusive volcanism, which is thought to be less than 0.25. Plate tectonics would certainly have an advantage by working even for more evolved planets. A simple, most-used concept of habitability requires the thermodynamic stability of liquid water on the surface of a planet. Cycling of CO2between the atmosphere, oceans and interior through subduction and surface volcanism is an important element of the carbonate-silicate cycle, a thermostat feedback cycle that will keep the atmosphere from entering into a runaway greenhouse. Calculations for a model Earth lacking plate tectonics but degassing CO2, N, and H2O to form a surface ocean and a secondary atmosphere (Tosi et al, 2016) suggest that liquid water can be maintained on the surface for 4.5Ga. The model planet would then qualify as habitable. It is conceivable that the CO2 buffering capability of its ocean together with silicate weathering of possible land surfaces and a biosphere could set up a CO2 sink that would further stabilize the temperature. As long as the planet keeps degassing CO2 at a sufficient rate, CO2 recycling through the mantle may not be required. However, this would require a sufficiently oxidized planet early on. If not sufficiently oxidized during accretion and core formation, oxidization of the planet would require cycling of matter between surface and interior reservoirs. Oxidization of an initially reduced Earth interior with the help of plate tectonics has been cited as a possible mechanism to allow the building up of oxygen in the terrestrial atmosphere around 2.3Ga b.p. (e.g., Catling and Claire, 2005), a pre-requisite for more evolved eukaryotic life. The oxidization would diminish a sink in the oxygen budget of the atmosphere by lowering the rate of outgassing of chemically reducing gases from the interior. Clearly, plate tectonics is a mechanism more potent of keeping a planet habitable and allow evolution of the biosphere than alternative concepts such as crust delamination. Catling, DC, Claire DW (2005), EPSL, 237, 1-20 Elkins-Tanton, L (2015) AGU Fall Meeting Abstract Tosi, N et al. (2016) EGU Abstract

Structural transformations in high-capacity Li 2Cu 0.5Ni 0.5O 2 cathodes

DOE PAGES

Ruther, Rose E.; Pandian, Amaresh Samuthira; Yan, Pengfei; ...

2017-03-09

Cathode materials that can cycle >1 Li + per transition metal are of substantial interest for increasing the overall energy density of lithium-ion batteries. Li 2Cu 0.5Ni 0.5O 2 has a very high theoretical capacity of ~500 mAh/g assuming both Li+ ions are cycled reversibly. The Cu 2+/3+ and Ni 2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li 2Cu 0.5Ni 0.5O 2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen evolves before the Cumore » 2+/3+ or Ni 3+/4+ transitions are accessed. In this contribution, X-ray diffraction, transmission electron microscopy (TEM), and transmission X-ray microscopy combined with X-ray absorption near edge structure (TXM–XANES) are used to follow the chemical and structural changes that occur in Li 2Cu 0.5Ni 0.5O 2 during electrochemical cycling. Li 2Cu 0.5Ni 0.5O 2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the changes that the Li 2NiO 2 endmember undergoes. Li 2Cu 0.5Ni 0.5O 2 loses long-range order during charge, but TEM analysis provides clear evidence of particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM–XANES are used to map the different phases that emerge during cycling ex situ and in situ. Lastly, significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.« less

Oxygen suppresses light-driven anodic current generation by a mixed phototrophic culture.

PubMed

Darus, Libertus; Ledezma, Pablo; Keller, Jürg; Freguia, Stefano

2014-12-02

This paper describes the detrimental effect of photosynthetically evolved oxygen on anodic current generation in the presence of riboflavin upon illumination of a mixed phototrophic culture enriched from a freshwater pond at +0.6 V vs standard hydrogen electrode. In the presence of riboflavin, the phototrophic biomass in the anodic compartment produced an electrical current in response to light/dark cycles (12 h/12 h) over 12 months of operation, generating a maximum current density of 17.5 mA x m(-2) during the dark phase, whereas a much lower current of approximately 2 mA x m(-2) was generated during illumination. We found that the low current generation under light exposure was caused by high rates of reoxidation of reduced riboflavin by oxygen produced during photosynthesis. Quantification of biomass by fluorescence in situ hybridization images suggested that green algae were predominant in both the anode-based biofilm (55.1%) and the anolyte suspension (87.9%) with the remaining biovolume accounted for by bacteria. Genus-level sequencing analysis revealed that bacteria were dominated by cyanobacterium Leptolyngbia (∼35%), while the prevailing algae were Dictyosphaerium, Coelastrum, and Auxenochlorella. This study offers a key comprehension of mediator sensitivity to reoxidation by dissolved oxygen for improvement of microbial solar cell performance.

Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

DOE PAGES

Liu, Haodong; An, Ke; Venkatachalam, Subramanian; ...

2016-04-06

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Li x/3Ni (3/8-3x/8)Co (1/4-x/4)Mn (3/8+7x/24)O 2 (x = 0.6, HLR) and low Li-rich Li(Li x/3Ni (1/3-x/3)Co (1/3-x/3)Mn(1/3+x/3)O 2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the endmore » of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.« less

Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

DOE PAGES

Wang, Xue; Choi, Sang-Il; Roling, Luke T.; ...

2015-07-02

Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can bemore » attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

Electronic structure of the Mn4OxCa cluster in the S0 and S2 states of the oxygen-evolving complex of photosystem II based on pulse 55Mn-ENDOR and EPR spectroscopy.

PubMed

Kulik, Leonid V; Epel, Boris; Lubitz, Wolfgang; Messinger, Johannes

2007-11-07

The heart of the oxygen-evolving complex (OEC) of photosystem II is a Mn4OxCa cluster that cycles through five different oxidation states (S0 to S4) during the light-driven water-splitting reaction cycle. In this study we interpret the recently obtained 55Mn hyperfine coupling constants of the S0 and S2 states of the OEC [Kulik et al. J. Am. Chem. Soc. 2005, 127, 2392-2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a "structure filter" that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821-825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 A Mn-Mn distance in S0 to 2.75 A in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459-7471] corresponds to a deprotonation of a mu-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the mu3-oxo bridged moiety of the cluster. We summarize our results in a molecular model for the S0 --> S1 and S1 --> S2 transitions.

An Intrinsically Disordered Photosystem II Subunit, PsbO, Provides a Structural Template and a Sensor of the Hydrogen-bonding Network in Photosynthetic Water Oxidation*

PubMed Central

Offenbacher, Adam R.; Polander, Brandon C.; Barry, Bridgette A.

2013-01-01

Photosystem II (PSII) is a membrane-bound enzyme that utilizes solar energy to catalyze the photooxidation of water. Molecular oxygen is evolved after four sequential light-driven oxidation reactions at the Mn4CaO5 oxygen-evolving complex, producing five sequentially oxidized states, Sn. PSII is composed of 17 membrane-spanning subunits and three extrinsic subunits, PsbP, PsbQ, and PsbO. PsbO is intrinsically disordered and plays a role in facilitation of the water oxidizing cycle. Native PsbO can be removed and substituted with recombinant PsbO, thereby restoring steady-state activity. In this report, we used reaction-induced Fourier transform infrared spectroscopy to obtain information concerning the role of PsbP, PsbQ, and PsbO during the S state cycle. Light-minus-dark difference spectra were acquired, monitoring structural changes associated with each accessible flash-induced S state transition in a highly purified plant PSII preparation (Triton X-100, octylthioglucoside). A comparison of S2 minus S1 spectra revealed that removal of PsbP and PsbQ had no significant effect on the data, whereas amide frequency and intensity changes were associated with PsbO removal. These data suggest that PsbO acts as an organizational template for the PSII reaction center. To identify any coupled conformational changes arising directly from PsbO, global 13C-PsbO isotope editing was employed. The reaction-induced Fourier transform infrared spectra of accessible S states provide evidence that PsbO spectral contributions are temperature (263 and 277 K) and S state dependent. These experiments show that PsbO undergoes catalytically relevant structural dynamics, which are coupled over long distance to hydrogen-bonding changes at the Mn4CaO5 cluster. PMID:23940038

Oxygen, the lead actor in the pathophysiologic drama: enactment of the trinity of normoxia, hypoxia, and hyperoxia in disease and therapy.

PubMed

Kulkarni, Aditi C; Kuppusamy, Periannan; Parinandi, Narasimham

2007-10-01

Aerobic life has evolved a dependence on molecular oxygen for its mere survival. Mitochondrial oxidative phosphorylation absolutely requires oxygen to generate the currency of energy in aerobes. The physiologic homeostasis of these organisms is strictly maintained by optimal cellular and tissue-oxygenation status through complex oxygen-sensing mechanisms, signaling cascades, and transport processes. In the event of fluctuating oxygen levels leading to either an increase (hyperoxia) or decrease (hypoxia) in cellular oxygen, the organism faces a crisis involving depletion of energy reserves, altered cell-signaling cascades, oxidative reactions/events, and cell death or tissue damage. Molecular oxygen is activated by both nonenzymatic and enzymatic mechanisms into highly reactive oxygen species (ROS). Aerobes have evolved effective antioxidant defenses to counteract the reactivity of ROS. Although the ROS are also required for many normal physiologic functions of the aerobes, overwhelming production of ROS coupled with their insufficient scavenging by endogenous antioxidants will lead to detrimental oxidative stress. Needless to say, molecular oxygen is at the center of oxygenation, oxidative phosphorylation, and oxidative stress. This review focuses on the biology and pathophysiology of oxygen, with an emphasis on transport, sensing, and activation of oxygen, oxidative phosphorylation, oxygenation, oxidative stress, and oxygen therapy.

p-capture reaction cycles in rotating massive stars and their impact on elemental abundances in globular cluster stars: A case study of O, Na and Al

NASA Astrophysics Data System (ADS)

Mahanta, Upakul; Goswami, Aruna; Duorah, Hiralal; Duorah, Kalpana

2017-08-01

Elemental abundance patterns of globular cluster stars can provide important clues for understanding cluster formation and early chemical evolution. The origin of the abundance patterns, however, still remains poorly understood. We have studied the impact of p-capture reaction cycles on the abundances of oxygen, sodium and aluminium considering nuclear reaction cycles of carbon-nitrogen-oxygen-fluorine, neon-sodium and magnesium-aluminium in massive stars in stellar conditions of temperature range 2×107 to 10×107 K and typical density of 102 gm cc-1. We have estimated abundances of oxygen, sodium and aluminium with respect to Fe, which are then assumed to be ejected from those stars because of rotation reaching a critical limit. These ejected abundances of elements are then compared with their counterparts that have been observed in some metal-poor evolved stars, mainly giants and red giants, of globular clusters M3, M4, M13 and NGC 6752. We observe an excellent agreement with [O/Fe] between the estimated and observed abundance values for globular clusters M3 and M4 with a correlation coefficient above 0.9 and a strong linear correlation for the remaining two clusters with a correlation coefficient above 0.7. The estimated [Na/Fe] is found to have a correlation coefficient above 0.7, thus implying a strong correlation for all four globular clusters. As far as [Al/Fe] is concerned, it also shows a strong correlation between the estimated abundance and the observed abundance for globular clusters M13 and NGC 6752, since here also the correlation coefficient is above 0.7 whereas for globular cluster M4 there is a moderate correlation found with a correlation coefficient above 0.6. Possible sources of these discrepancies are discussed.

Evaluating climatic response to external radiative forcing during the late Miocene to early Pliocene: New perspectives from eastern equatorial Pacific (IODP U1338) and North Atlantic (ODP 982) locations

NASA Astrophysics Data System (ADS)

Drury, Anna Joy; John, Cédric M.; Shevenell, Amelia E.

2016-01-01

Orbital-scale climate variability during the latest Miocene-early Pliocene is poorly understood due to a lack of high-resolution records spanning 8.0-3.5 Ma, which resolve all orbital cycles. Assessing this variability improves understanding of how Earth's system sensitivity to insolation evolves and provides insight into the factors driving the Messinian Salinity Crisis (MSC) and the Late Miocene Carbon Isotope Shift (LMCIS). New high-resolution benthic foraminiferal Cibicidoides mundulus δ18O and δ13C records from equatorial Pacific International Ocean Drilling Program Site U1338 are correlated to North Atlantic Ocean Drilling Program Site 982 to obtain a global perspective. Four long-term benthic δ18O variations are identified: the Tortonian-Messinian, Miocene-Pliocene, and Early-Pliocene Oxygen Isotope Lows (8-7, 5.9-4.9, and 4.8-3.5 Ma) and the Messinian Oxygen Isotope High (MOH; 7-5.9 Ma). Obliquity-paced variability dominates throughout, except during the MOH. Eleven new orbital-scale isotopic stages are identified between 7.4 and 7.1 Ma. Cryosphere and carbon cycle sensitivities, estimated from δ18O and δ13C variability, suggest a weak cryosphere-carbon cycle coupling. The MSC termination coincided with moderate cryosphere sensitivity and reduced global ice sheets. The LMCIS coincided with reduced carbon cycle sensitivity, suggesting a driving force independent of insolation changes. The response of the cryosphere and carbon cycle to obliquity forcing is established, defined as Earth System Response (ESR). Observations reveal that two late Miocene-early Pliocene climate states existed. The first is a prevailing dynamic state with moderate ESR and obliquity-driven Antarctic ice variations, associated with reduced global ice volumes. The second is a stable state, which occurred during the MOH, with reduced ESR and lower obliquity-driven variability, associated with expanded global ice volumes.

Process for photosynthetically splitting water

DOEpatents

Greenbaum, Elias

1984-01-01

The invention is an improved process for producing gaseous hydrogen and oxygen from water. The process is conducted in a photolytic reactor which contains a water-suspension of a photoactive material containing a hydrogen-liberating catalyst. The reactor also includes a volume for receiving gaseous hydrogen and oxygen evolved from the liquid phase. To avoid oxygen-inactivation of the catalyst, the reactor is evacuated continuously by an external pump which circulates the evolved gases through means for selectively recovering hydrogen therefrom. The pump also cools the reactor by evaporating water from the liquid phase. Preferably, product recovery is effected by selectively diffusing the hydrogen through a heated semipermeable membrane, while maintaining across the membrane a magnetic field gradient which biases the oxygen away from the heated membrane. This promotes separation, minimizes the back-reaction of hydrogen and oxygen, and protects the membrane.

[Origin of the oxygen detected by the Viking stations in an analysis of Mars soil].

PubMed

Imshenetskiĭ, A A; Murzakov, B G; Dorofeeva, I K

1978-01-01

Reactions between the mineral limonite and hydrogen peroxide were studied and gases produced thereupon were analysed by gas chromatography. Oxygen did not evolve if limonite was added to hydrogen peroxide frozen at a temperature of dry ice. However, at room temperature, a vigorous chemical reaction occurred and a large amount of oxygen evolved. Apparently, the ground of Mars contains not only hydrated iron oxides but also frozen hydrogen peroxide whose thawing in the incubation chamber of Viking resulted in its catalytic degradation under the action of iron ions. The evidence thus obtained and its comparison with the data of American scientists account for considerable evolution of oxygen detected by Viking upon analysis of the Mars ground.

The oxygen paradox of neurovascular coupling

PubMed Central

Leithner, Christoph; Royl, Georg

2014-01-01

The coupling of cerebral blood flow (CBF) to neuronal activity is well preserved during evolution. Upon changes in the neuronal activity, an incompletely understood coupling mechanism regulates diameter changes of supplying blood vessels, which adjust CBF within seconds. The physiologic brain tissue oxygen content would sustain unimpeded brain function for only 1 second if continuous oxygen supply would suddenly stop. This suggests that the CBF response has evolved to balance oxygen supply and demand. Surprisingly, CBF increases surpass the accompanying increases of cerebral metabolic rate of oxygen (CMRO2). However, a disproportionate CBF increase may be required to increase the concentration gradient from capillary to tissue that drives oxygen delivery. However, the brain tissue oxygen content is not zero, and tissue pO2 decreases could serve to increase oxygen delivery without a CBF increase. Experimental evidence suggests that CMRO2 can increase with constant CBF within limits and decreases of baseline CBF were observed with constant CMRO2. This conflicting evidence may be viewed as an oxygen paradox of neurovascular coupling. As a possible solution for this paradox, we hypothesize that the CBF response has evolved to safeguard brain function in situations of moderate pathophysiological interference with oxygen supply. PMID:24149931

[What degree of hypoxemia is tolerable for human beings?].

PubMed

Köhler, D

2010-03-01

According to the literature, hypoxemia is considered to be severe when oxygen saturation (Sa O(2)) falls below 90 %. Frequently one can discover lower values without impairment of the patient. Especially patients with the obesity hypoventilation syndrome (OHS) will have frequent night time desaturations of significant duration below 50 % Sa O(2), but do still cope with their daytime jobs. This discrepancy can only be explained by the fact, that hypoxemia is not equivalent to tissue hypoxia. The latter is mainly being determined by oxygen delivery (DO2) which is being calculated by multiplying cardiac output (CO) and oxygen content (CaO2). Ca O(2) is determined by the product of Sa O(2) and haemoglobin (Hb) times 1.35. From this context it becomes evident, that assessing hypoxemia without considering oxygen content will frequently be misleading. The human organism has several possible ways of compensation in order to avoid tissue hypoxia. In case of acute hypoxemia that evolves within minutes the organism can shift the oxygen binding curve by changing 2 - 3-DGP erythrocytic activity. Additionally non vital organ systems might reduce their oxygen uptake. During sustained hypoxia (lasting 2 - 3 days) the Krebs cycle and the respiratory chain will express hypoxia-resistant iso-enzymes. Long lasting hypoxia can be compensated by polycythemia. Indirect data suggest, that the critical number for the oxygen content is rather low and is estimated to be somewhere around 33 % of the normal value. These mechanism of hypoxia-resistance are hardly ever maxed out in patients on critical care units.Lack of knowledge of the above described mechanisms does frequently result in diseases like ARDS which frequently develops due to excessive ventilatory pressures and excessive inspired O(2) concentrations. Georg Thieme Verlag KG Stuttgart, New York.

Mass-loss rates and luminosities of evolved stars in the Magellanic Clouds .

NASA Astrophysics Data System (ADS)

Groenewegen, M. A. T.; Sloan, G. C.

Stars on the asymptotic giant branch (AGB) stars play an important role in the chemical evolution of their host galaxies and the life cycle of dust in the interstellar medium. A detailed and quantitative understanding of they lose mass and eject their envelopes remains elusive, particularly how that process depends on metallicity. Groenewegen & Sloan (2017, hereafter GS17) recently presented dust radiative transfer models for 225 carbon stars and 171 oxygen-rich evolved stars in the Magellanic Clouds and four nearby dSphs which were observed with the Infrared spectrograph on the Spitzer Space Telescope. They applied a minimisation procedure to fit models to spectral energy distributions constructed from the infrared spectra and the available optical and infrared photometry for each star to determine its luminosity and dust mass-loss rate (MLR). In this contribution two items from that paper are highlighted: an update on MSX SMC 055, which Groenewegen et al. (2009) suggested could be a super-AGB star, and a discussion of synthetic colour-colour and colour-magnitude diagrams expected from the James Webb Space Telescope.

Evolution of the 3-hydroxypropionate bicycle and recent transfer of anoxygenic photosynthesis into the Chloroflexi

NASA Astrophysics Data System (ADS)

Shih, Patrick M.; Ward, Lewis M.; Fischer, Woodward W.

2017-10-01

Various lines of evidence from both comparative biology and the geologic record make it clear that the biochemical machinery for anoxygenic photosynthesis was present on early Earth and provided the evolutionary stock from which oxygenic photosynthesis evolved ca. 2.3 billion years ago. However, the taxonomic identity of these early anoxygenic phototrophs is uncertain, including whether or not they remain extant. Several phototrophic bacterial clades are thought to have evolved before oxygenic photosynthesis emerged, including the Chloroflexi, a phylum common across a wide range of modern environments. Although Chloroflexi have traditionally been thought to be an ancient phototrophic lineage, genomics has revealed a much greater metabolic diversity than previously appreciated. Here, using a combination of comparative genomics and molecular clock analyses, we show that phototrophic members of the Chloroflexi phylum are not particularly ancient, having evolved well after the rise of oxygen (ca. 867 million years ago), and thus cannot be progenitors of oxygenic photosynthesis. Similarly, results show that the carbon fixation pathway that defines this clade—the 3-hydroxypropionate bicycle—evolved late in Earth history as a result of a series of horizontal gene transfer events, explaining the lack of geological evidence for this pathway based on the carbon isotope record. These results demonstrate the role of horizontal gene transfer in the recent metabolic innovations expressed within this phylum, including its importance in the development of a novel carbon fixation pathway.

In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

PubMed Central

Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

2013-01-01

Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an “electron reservoir”, we suggest that rGO serves as “peroxide cleaner” in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

Sulfur cycling in plays an important role in the development of Ocean Anoxic Events

NASA Astrophysics Data System (ADS)

Gomes, M. L.; Raven, M. R.; Fike, D. A.; Gill, B. C.; Johnston, D. T.

2017-12-01

Ocean Anoxic Events (OAEs) are major carbon cycle perturbations marked by enhanced organic carbon deposition in the marine realm and carbon isotope excursions in organic and inorganic carbon. Although not as severe as the "big five" mass extinctions, OAEs had dire consequences for marine ecosystems and thus influenced Mesozoic evolutionary patterns. Sulfur cycle reconstructions provide insight into the biogeochemical processes that played a role in the development of OAEs because the sulfur cycle is linked with the carbon and oxygen cycles. We present sulfur and oxygen isotope records from carbonate-associated sulfate from the Toarcian OAE that documents a positive sulfate-oxygen isotope excursion of +6‰, which is similar to the magnitude of the positive sulfur isotope excursion documented at the same site and other globally distributed sites. This high-resolution record allows us to explore temporal variability in the onset of the isotopic excursions: the onset of the positive sulfate-oxygen isotope excursion occurs at the same stratigraphic interval as the onset of the positive carbon isotope excursion and both precede the onset of the positive sulfate-sulfur isotope excursion. Because oxygen is rapidly recycled during oxidative sulfur cycling, changes in oxidative sulfur cycling affect oxygen isotope values of sulfate without impacting sulfur isotope values. Thus, the early onset of the sulfate-oxygen isotope excursion implies a change in oxidative sulfur cycling, which is likely due to a shoaling of the zone of sulfate reduction. We explore the consequences of sulfate reduction zone shoaling for organic carbon preservation. Specifically, the sulfurization of organic matter, which makes organic matter less susceptible to degradation, occurs more rapidly when the top of the zone of sulfate reduction is near or above the sediment water interface. Therefore, we suggest that the shoaling of the sulfate reduction zone locally changed pathways of oxidative sulfur cycling and enhanced organic carbon preservation. Given synchronous changes in similar, globally-distributed depositional environments, this impacted the global biogeochemical cycles of oxygen, carbon, and nutrients in ways that sustained decreased oxygen availability and influenced extinction patterns of marine organisms.

The prefrontal oxygenation and ventilatory responses at start of one-legged cycling exercise have relation to central command.

PubMed

Asahara, Ryota; Matsukawa, Kanji; Ishii, Kei; Liang, Nan; Endo, Kana

2016-11-01

When performing exercise arbitrarily, activation of central command should start before the onset of exercise, but when exercise is forced to start with cue, activation of central command should be delayed. We examined whether the in-advance activation of central command influenced the ventilatory response and reflected in the prefrontal oxygenation, by comparing the responses during exercise with arbitrary and cued start. The breath-by-breath respiratory variables and the prefrontal oxygenated-hemoglobin concentration (Oxy-Hb) were measured during one-legged cycling. Minute ventilation (V̇e) at the onset of arbitrary one-legged cycling was augmented to a greater extent than cued cycling, while end-tidal carbon dioxide tension (ETco 2 ) decreased irrespective of arbitrary or cued start. Symmetric increase in the bilateral prefrontal Oxy-Hb occurred before and at the onset of arbitrary one-legged cycling, whereas such an increase was absent with cued start. The time course and magnitude of the increased prefrontal oxygenation were not influenced by the extent of subjective rating of perceived exertion and were the same as those of the prefrontal oxygenation during two-legged cycling previously reported. Mental imagery or passive performance of the one-legged cycling increased V̇e and decreased ETco 2 Neither intervention, however, augmented the prefrontal Oxy-Hb. The changes in ETco 2 could not explain the prefrontal oxygenation response during voluntary or passive one-legged cycling. Taken together, it is likely that the in-advance activation of central command influenced the ventilatory response by enhancing minute ventilation at the onset of one-legged cycling exercise and reflected in the preexercise increase in the prefrontal oxygenation. Copyright © 2016 the American Physiological Society.

Design Evolution of the Wide Field Infrared Survey Telescope using Astrophysics Focused Telescope Assets (WFIRST-AFTA) and Lessons Learned

NASA Technical Reports Server (NTRS)

Peabody, Hume; Peters, Carlton; Rodriguez, Juan; McDonald, Carson; Content, David A.; Jackson, Cliff

2015-01-01

The design of the Wide Field Infrared Survey Telescope using Astrophysics Focused Telescope Assets (WFIRST-AFTA) continues to evolve as each design cycle is analyzed. In 2012, two Hubble sized (2.4 m diameter) telescopes were donated to NASA from elsewhere in the Federal Government. NASA began investigating potential uses for these telescopes and identified WFIRST as a mission to benefit from these assets. With an updated, deeper, and sharper field of view than previous design iterations with a smaller telescope, the optical designs of the WFIRST instruments were updated and the mechanical and thermal designs evolved around the new optical layout. Beginning with Design Cycle 3, significant analysis efforts yielded a design and model that could be evaluated for Structural-Thermal-Optical-Performance (STOP) purposes for the Wide Field Imager (WFI) and provided the basis for evaluating the high level observatory requirements. Development of the Cycle 3 thermal model provided some valuable analysis lessons learned and established best practices for future design cycles. However, the Cycle 3 design did include some major liens and evolving requirements which were addressed in the Cycle 4 Design. Some of the design changes are driven by requirements changes, while others are optimizations or solutions to liens from previous cycles. Again in Cycle 4, STOP analysis was performed and further insights into the overall design were gained leading to the Cycle 5 design effort currently underway. This paper seeks to capture the thermal design evolution, with focus on major design drivers, key decisions and their rationale, and lessons learned as the design evolved.

Design Evolution of the Wide Field Infrared Survey Telescope Using Astrophysics Focused Telescope Assets (WFIRST-AFTA) and Lessons Learned

NASA Technical Reports Server (NTRS)

Peabody, Hume L.; Peters, Carlton V.; Rodriguez-Ruiz, Juan E.; McDonald, Carson S.; Content, David A.; Jackson, Clifton E.

2015-01-01

The design of the Wide Field Infrared Survey Telescope using Astrophysics Focused Telescope Assets (WFIRST-AFTA) continues to evolve as each design cycle is analyzed. In 2012, two Hubble sized (2.4 m diameter) telescopes were donated to NASA from elsewhere in the Federal Government. NASA began investigating potential uses for these telescopes and identified WFIRST as a mission to benefit from these assets. With an updated, deeper, and sharper field of view than previous design iterations with a smaller telescope, the optical designs of the WFIRST instruments were updated and the mechanical and thermal designs evolved around the new optical layout. Beginning with Design Cycle 3, significant analysis efforts yielded a design and model that could be evaluated for Structural-Thermal-Optical-Performance (STOP) purposes for the Wide Field Imager (WFI) and provided the basis for evaluating the high level observatory requirements. Development of the Cycle 3 thermal model provided some valuable analysis lessons learned and established best practices for future design cycles. However, the Cycle 3 design did include some major liens and evolving requirements which were addressed in the Cycle 4 Design. Some of the design changes are driven by requirements changes, while others are optimizations or solutions to liens from previous cycles. Again in Cycle 4, STOP analysis was performed and further insights into the overall design were gained leading to the Cycle 5 design effort currently underway. This paper seeks to capture the thermal design evolution, with focus on major design drivers, key decisions and their rationale, and lessons learned as the design evolved.

Metal availability and the expanding network of microbial metabolisms in the Archaean eon

NASA Astrophysics Data System (ADS)

Moore, Eli K.; Jelen, Benjamin I.; Giovannelli, Donato; Raanan, Hagai; Falkowski, Paul G.

2017-09-01

Life is based on energy gained by electron-transfer processes; these processes rely on oxidoreductase enzymes, which often contain transition metals in their structures. The availability of different metals and substrates has changed over the course of Earth's history as a result of secular changes in redox conditions, particularly global oxygenation. New metabolic pathways using different transition metals co-evolved alongside changing redox conditions. Sulfur reduction, sulfate reduction, methanogenesis and anoxygenic photosynthesis appeared between about 3.8 and 3.4 billion years ago. The oxidoreductases responsible for these metabolisms incorporated metals that were readily available in Archaean oceans, chiefly iron and iron-sulfur clusters. Oxygenic photosynthesis appeared between 3.2 and 2.5 billion years ago, as did methane oxidation, nitrogen fixation, nitrification and denitrification. These metabolisms rely on an expanded range of transition metals presumably made available by the build-up of molecular oxygen in soil crusts and marine microbial mats. The appropriation of copper in enzymes before the Great Oxidation Event is particularly important, as copper is key to nitrogen and methane cycling and was later incorporated into numerous aerobic metabolisms. We find that the diversity of metals used in oxidoreductases has increased through time, suggesting that surface redox potential and metal incorporation influenced the evolution of metabolism, biological electron transfer and microbial ecology.

Final Technical Report - Use of Systems Biology Approaches to Develop Advanced Biofuel-Synthesizing Cyanobacterial Strains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pakrasi, Himadri

The overall objective of this project was to use a systems biology approach to evaluate the potentials of a number of cyanobacterial strains for photobiological production of advanced biofuels and/or their chemical precursors. Cyanobacteria are oxygen evolving photosynthetic prokaryotes. Among them, certain unicellular species such as Cyanothece can also fix N 2, a process that is exquisitely sensitive to oxygen. To accommodate such incompatible processes in a single cell, Cyanothece produces oxygen during the day, and creates an O 2-limited intracellular environment during the night to perform O 2-sensitive processes such as N 2-fixation. Thus, Cyanothece cells are natural bioreactorsmore » for the storage of captured solar energy with subsequent utilization at a different time during a diurnal cycle. Our studies include the identification of a novel, fast-growing, mixotrophic, transformable cyanobacterium. This strain has been sequenced and will be made available to the community. In addition, we have developed genome-scale models for a family of cyanobacteria to assess their metabolic repertoire. Furthermore, we developed a method for rapid construction of metabolic models using multiple annotation sources and a metabolic model of a related organism. This method will allow rapid annotation and screening of potential phenotypes based on the newly available genome sequences of many organisms.« less

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

2017-03-01

Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life, and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

Amorphous manganese-calcium oxides as a possible evolutionary origin for the CaMn₄ cluster in photosystem II.

PubMed

Najafpour, Mohammad Mahdi

2011-06-01

In this paper a few calcium-manganese oxides and calcium-manganese minerals are studied as catalysts for water oxidation. The natural mineral marokite is also studied as a catalyst for water oxidation for the first time. Marokite is made up of edge-sharing Mn(3+) in a distorted octahedral environment and eight-coordinate Ca(2+) centered polyhedral layers. The structure is similar to recent models of the oxygen evolving complex in photosystem II. Thus, the oxygen evolving complex in photosystem II does not have an unusual structure and could be synthesized hydrothermally. Also in this paper, oxygen evolution is studied with marokite (CaMn₂O₄), pyrolusite (MnO₂) and compared with hollandite (Ba(0.2)Ca(0.15)K(0.3)Mn(6.9)Al(0.2)Si(0.3)O(16)), hausmannite (Mn₃O₄), Mn₂O₃.H₂O, Ca Mn₃O₆.H₂O, CaMn₄O₈.H₂O, CaMn₂O₄.H₂O and synthetic marokite (CaMn₂O₄). I propose that the origin of the oxygen evolving complex in photosystem II resulted from absorption of calcium and manganese ions that were precipitated together in the archean oceans by protocyanobacteria because of changing pH from ~5 to ~8-10. As reported in this paper, amorphous calcium-manganese oxides with different ratios of manganese and calcium are effective catalysts for water oxidation. The bond types and lengths of the calcium and manganese ions in the calcium-manganese oxides are directly comparable to those in the OEC. This primitive structure of these amorphous calcium-manganese compounds could be changed and modified by environmental groups (amino acids) to form the oxygen evolving complex in photosystem II.

Evolution of the 3-hydroxypropionate bicycle and recent transfer of anoxygenic photosynthesis into the Chloroflexi

DOE PAGES

Shih, Patrick M.; Ward, Lewis M.; Fischer, Woodward W.

2017-09-18

We report various lines of evidence from both comparative biology and the geologic record make it clear that the biochemical machinery for anoxygenic photosynthesis was present on early Earth and provided the evolutionary stock from which oxygenic photosynthesis evolved ca. 2.3 billion years ago. However, the taxonomic identity of these early anoxygenic phototrophs is uncertain, including whether or not they remain extant. Several phototrophic bacterial clades are thought to have evolved before oxygenic photosynthesis emerged, including the Chloroflexi, a phylum common across a wide range of modern environments. Although Chloroflexi have traditionally been thought to be an ancient phototrophic lineage,more » genomics has revealed a much greater metabolic diversity than previously appreciated. Here, using a combination of comparative genomics and molecular clock analyses, we show that phototrophic members of the Chloroflexi phylum are not particularly ancient, having evolved well after the rise of oxygen (ca. 867 million years ago), and thus cannot be progenitors of oxygenic photosynthesis. Similarly, results show that the carbon fixation pathway that defines this clade—the 3-hydroxypropionate bicycle—evolved late in Earth history as a result of a series of horizontal gene transfer events, explaining the lack of geological evidence for this pathway based on the carbon isotope record. Finally, these results demonstrate the role of horizontal gene transfer in the recent metabolic innovations expressed within this phylum, including its importance in the development of a novel carbon fixation pathway.« less

Evolution of the 3-hydroxypropionate bicycle and recent transfer of anoxygenic photosynthesis into the Chloroflexi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shih, Patrick M.; Ward, Lewis M.; Fischer, Woodward W.

We report various lines of evidence from both comparative biology and the geologic record make it clear that the biochemical machinery for anoxygenic photosynthesis was present on early Earth and provided the evolutionary stock from which oxygenic photosynthesis evolved ca. 2.3 billion years ago. However, the taxonomic identity of these early anoxygenic phototrophs is uncertain, including whether or not they remain extant. Several phototrophic bacterial clades are thought to have evolved before oxygenic photosynthesis emerged, including the Chloroflexi, a phylum common across a wide range of modern environments. Although Chloroflexi have traditionally been thought to be an ancient phototrophic lineage,more » genomics has revealed a much greater metabolic diversity than previously appreciated. Here, using a combination of comparative genomics and molecular clock analyses, we show that phototrophic members of the Chloroflexi phylum are not particularly ancient, having evolved well after the rise of oxygen (ca. 867 million years ago), and thus cannot be progenitors of oxygenic photosynthesis. Similarly, results show that the carbon fixation pathway that defines this clade—the 3-hydroxypropionate bicycle—evolved late in Earth history as a result of a series of horizontal gene transfer events, explaining the lack of geological evidence for this pathway based on the carbon isotope record. Finally, these results demonstrate the role of horizontal gene transfer in the recent metabolic innovations expressed within this phylum, including its importance in the development of a novel carbon fixation pathway.« less

PEM regenerative fuel cells

NASA Technical Reports Server (NTRS)

Swette, Larry L.; Laconti, Anthony B.; Mccatty, Stephen A.

1993-01-01

This paper will update the progress in developing electrocatalyst systems and electrode structures primarily for the positive electrode of single-unit solid polymer proton exchange membrane (PEM) regenerative fuel cells. The work was done with DuPont Nafion 117 in complete fuel cells (40 sq cm electrodes). The cells were operated alternately in fuel cell mode and electrolysis mode at 80 C. In fuel cell mode, humidified hydrogen and oxygen were supplied at 207 kPa (30 psi); in electrolysis mode, water was pumped over the positive electrode and the gases were evolved at ambient pressure. Cycling data will be presented for Pt-Ir catalysts and limited bifunctional data will be presented for Pt, Ir, Ru, Rh, and Na(x)Pt3O4 catalysts as well as for electrode structure variations.

Earth’s oxygen cycle and the evolution of animal life

PubMed Central

Reinhard, Christopher T.; Planavsky, Noah J.; Olson, Stephanie L.; Lyons, Timothy W.; Erwin, Douglas H.

2016-01-01

The emergence and expansion of complex eukaryotic life on Earth is linked at a basic level to the secular evolution of surface oxygen levels. However, the role that planetary redox evolution has played in controlling the timing of metazoan (animal) emergence and diversification, if any, has been intensely debated. Discussion has gravitated toward threshold levels of environmental free oxygen (O2) necessary for early evolving animals to survive under controlled conditions. However, defining such thresholds in practice is not straightforward, and environmental O2 levels can potentially constrain animal life in ways distinct from threshold O2 tolerance. Herein, we quantitatively explore one aspect of the evolutionary coupling between animal life and Earth’s oxygen cycle—the influence of spatial and temporal variability in surface ocean O2 levels on the ecology of early metazoan organisms. Through the application of a series of quantitative biogeochemical models, we find that large spatiotemporal variations in surface ocean O2 levels and pervasive benthic anoxia are expected in a world with much lower atmospheric pO2 than at present, resulting in severe ecological constraints and a challenging evolutionary landscape for early metazoan life. We argue that these effects, when considered in the light of synergistic interactions with other environmental parameters and variable O2 demand throughout an organism’s life history, would have resulted in long-term evolutionary and ecological inhibition of animal life on Earth for much of Middle Proterozoic time (∼1.8–0.8 billion years ago). PMID:27457943

Hydrodynamic models for novae with ejecta rich in oxygen, neon and magnesium

NASA Technical Reports Server (NTRS)

Starrfield, S.; Sparks, W. M.; Truran, J. W.

1985-01-01

The characteristics of a new class of novae are identified and explained. This class consists of those objects that have been observed to eject material rich in oxygen, neon, magnesium, and aluminum at high velocities. We propose that for this class of novae the outburst is occurring not on a carbon-oxygen white dwarf but on an oxygen-neon-magnesium white dwarf which has evolved from a star which had a main sequence mass of approx. 8 solar masses to approx. 12 solar masses. An outburst was simulated by evolving 1.25 solar mass white dwarfs accreting hydrogen rich material at various rates. The effective enrichment of the envelope by ONeMg material from the core is simulated by enhancing oxygen in the accreted layers. The resulting evolutionary sequences can eject the entire accreted envelope plus core material at high velocities. They can also become super-Eddington at maximum bolometric luminosity. The expected frequency of such events (approx. 1/4) is in good agreement with the observed numbers of these novae.

Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

DOEpatents

Cassano, Anthony A.

1985-01-01

A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

Evaluation of solid oxide fuel cell systems for electricity generation

NASA Technical Reports Server (NTRS)

Somers, E. V.; Vidt, E. J.; Grimble, R. E.

1982-01-01

Air blown (low BTU) gasification with atmospheric pressure Solid Electrolyte Fuel Cells (SOFC) and Rankine bottoming cycle, oxygen blown (medium BTU) gasification with atmospheric pressure SOFC and Rankine bottoming cycle, air blown gasification with pressurized SOFC and combined Brayton/Rankine bottoming cycle, oxygen blown gasification with pressurized SOFC and combined Brayton/Rankine bottoming cycle were evaluated.

Simulation of the synergistic low Earth orbit effects of vacuum thermal cycling, vacuum UV radiation, and atomic oxygen

NASA Technical Reports Server (NTRS)

Dever, Joyce A.; Degroh, Kim K.; Stidham, Curtis R.; Stueber, Thomas J.; Dever, Therese M.; Rodriguez, Elvin; Terlep, Judith A.

1992-01-01

In order to assess the low Earth orbit (LEO) durability of candidate space materials, it is necessary to use ground laboratory facilities which provide LEO environmental effects. A facility combining vacuum thermal cycling and vacuum ultraviolet (VUV) radiation has been designed and constructed at NASA Lewis Research Center for this purpose. This facility can also be operated without the VUV lamps. An additional facility can be used to provide VUV exposure only. By utilizing these facilities, followed by atomic oxygen exposure in an RF plasma asher, the effects of the individual vacuum thermal cycling and VUV environments can be compared to the effect of the combined vacuum thermal cycling/VUV environment on the atomic oxygen durability of materials. The synergistic effects of simulated LEO environmental conditions on materials were evaluated by first exposing materials to vacuum thermal cycling, VUV, and vacuum thermal cycling/VUV environments followed by exposure to atomic oxygen in an RP plasma asher. Candidate space power materials such as atomic oxygen protected polyimides and solar concentrator mirrors were evaluated using these facilities. Characteristics of the Vacuum Thermal Cycling/VUV Exposure Facility which simulates the temperature sequences and solar ultraviolet radiation exposure that would be experienced by a spacecraft surface in LEO are discussed. Results of durability evaluations of some candidate space power materials to the simulated LEO environmental conditions will also be discussed. Such results have indicated that for some materials, atomic oxygen durability is affected by previous exposure to thermal cycling and/or VUV exposure.

Development of a Reactor for the Extraction of Oxygen and Volatiles From Lunar Regolith

NASA Technical Reports Server (NTRS)

Kleinhenz, Julie; Yuan, Zengguang; Sacksteder, Kurt; Caruso, John

2009-01-01

The RESOLVE (Regolith and Environment Science, Oxygen and Lunar Volatiles Extraction) Project, aims to extract and quantify useful resources from lunar soil. The reactor developed for RESOLVE is a dual purpose system, designed to evolve both water, at 150 C and up to 80 psig, and oxygen, using hydrogen reduction at 900 C. A variety of laboratory tests were performed to verify its operation and to explore the properties of the analog site soil. The results were also applied to modeling efforts which are being used to estimate the apparent thermal properties of the soil. The experimental and numerical results, along with the analog site tests, will be used to evolve and optimize future reactor designs.

How did life survive Earth's great oxygenation?

PubMed

Fischer, Woodward W; Hemp, James; Valentine, Joan Selverstone

2016-04-01

Life on Earth originated and evolved in anoxic environments. Around 2.4 billion-years-ago, ancestors of Cyanobacteria invented oxygenic photosynthesis, producing substantial amounts of O2 as a byproduct of phototrophic water oxidation. The sudden appearance of O2 would have led to significant oxidative stress due to incompatibilities with core cellular biochemical processes. Here we examine this problem through the lens of Cyanobacteria-the first taxa to observe significant fluxes of intracellular dioxygen. These early oxygenic organisms likely adapted to the oxidative stress by co-opting preexisting systems (exaptation) with fortuitous antioxidant properties. Over time more advanced antioxidant systems evolved, allowing Cyanobacteria to adapt to an aerobic lifestyle and become the most important environmental engineers in Earth history. Copyright © 2016 Elsevier Ltd. All rights reserved.

A unique mode of tissue oxygenation and the adaptive radiation of teleost fishes.

PubMed

Randall, D J; Rummer, J L; Wilson, J M; Wang, S; Brauner, C J

2014-04-15

Teleost fishes constitute 95% of extant aquatic vertebrates, and we suggest that this is related in part to their unique mode of tissue oxygenation. We propose the following sequence of events in the evolution of their oxygen delivery system. First, loss of plasma-accessible carbonic anhydrase (CA) in the gill and venous circulations slowed the Jacobs-Stewart cycle and the transfer of acid between the plasma and the red blood cells (RBCs). This ameliorated the effects of a generalised acidosis (associated with an increased capacity for burst swimming) on haemoglobin (Hb)-O2 binding. Because RBC pH was uncoupled from plasma pH, the importance of Hb as a buffer was reduced. The decrease in buffering was mediated by a reduction in the number of histidine residues on the Hb molecule and resulted in enhanced coupling of O2 and CO2 transfer through the RBCs. In the absence of plasma CA, nearly all plasma bicarbonate ultimately dehydrated to CO2 occurred via the RBCs, and chloride/bicarbonate exchange was the rate-limiting step in CO2 excretion. This pattern of CO2 excretion across the gills resulted in disequilibrium states for CO2 hydration/dehydration reactions and thus elevated arterial and venous plasma bicarbonate levels. Plasma-accessible CA embedded in arterial endothelia was retained, which eliminated the localized bicarbonate disequilibrium forming CO2 that then moved into the RBCs. Consequently, RBC pH decreased which, in conjunction with pH-sensitive Bohr/Root Hbs, elevated arterial oxygen tensions and thus enhanced tissue oxygenation. Counter-current arrangement of capillaries (retia) at the eye and later the swim bladder evolved along with the gas gland at the swim bladder. Both arrangements enhanced and magnified CO2 and acid production and, therefore, oxygen secretion to those specialised tissues. The evolution of β-adrenergically stimulated RBC Na(+)/H(+) exchange protected gill O2 uptake during stress and further augmented plasma disequilibrium states for CO2 hydration/dehydration. Finally, RBC organophosphates (e.g. NTP) could be reduced during hypoxia to further increase Hb-O2 affinity without compromising tissue O2 delivery because high-affinity Hbs could still adequately deliver O2 to the tissues via Bohr/Root shifts. We suggest that the evolution of this unique mode of tissue O2 transfer evolved in the Triassic/Jurassic Period, when O2 levels were low, ultimately giving rise to the most extensive adaptive radiation of extant vertebrates, the teleost fishes.

Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

DOEpatents

Cassano, A.A.

1985-07-02

A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

Metal oxidation states in biological water splitting.

PubMed

Krewald, Vera; Retegan, Marius; Cox, Nicholas; Messinger, Johannes; Lubitz, Wolfgang; DeBeer, Serena; Neese, Frank; Pantazis, Dimitrios A

2015-03-01

A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five S i states ( i = 0-4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called "high-valent scheme"-where, for example, the Mn oxidation states in the S 2 state are assigned as III, IV, IV, IV-the competing "low-valent scheme" that differs by a total of two metal unpaired electrons ( i.e. III, III, III, IV in the S 2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55 Mn ENDOR data of the S 2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S 0 (III, III, III, IV) to S 3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster.

Evolution of modern eukaryotes in the context of Cryogenian geochemical, tectonic and climatic changes (Invited)

NASA Astrophysics Data System (ADS)

Bosak, T.; MacDonald, F. A.; Pruss, S. B.; Lahr, D.

2010-12-01

The Cryogenian period (850-635 Ma) is one of the most dynamic periods in Earth history; its strata host evidence of the break-up of a super-continent, multiple low-latitude glaciations, the reorganization of geochemical cycles, the radiation of eukaryotes, and the origin of animals. However, relationships between the evolving ecosystems during this time, global glaciations and the cycling of carbon, sulfur and oxygen remain poorly understood. This is due to the lack of studies that couple geochemical and micropaleontological records in a stratigraphic and sedimentological context and the paucity of studies of sections that span the entire interval. Here we describe our current work on the recently discovered microfossil record from carbonate rocks deposited between the two Cryogenian low-latitude glaciations (710-635 million years ago) including the Tayshir Formation in Mongolia and cap carbonates from the Rasthof Formation in Namibia. This record provides constraints on the severity of Sturtian low-latitude glaciation and shows the presence of various modern eukaryotic lineages in late Cryogenian ecosystems and the first occurrences of various shell-building organisms. These biological changes gave rise to an increasing complexity of food webs that may have fed the first animals and influenced the sinking and burial of organic matter, ushering the Neoproterozoic revolution in biogeochemical cycling.

Enthalpy Changes during Photosynthetic Water Oxidation Tracked by Time-Resolved Calorimetry Using a Photothermal Beam Deflection Technique☆☆☆

PubMed Central

Krivanek, Roland; Dau, Holger; Haumann, Michael

2008-01-01

The energetics of the individual reaction steps in the catalytic cycle of photosynthetic water oxidation at the Mn4Ca complex of photosystem II (PSII) are of prime interest. We studied the electron transfer reactions in oxygen-evolving PSII membrane particles from spinach by a photothermal beam deflection technique, allowing for time-resolved calorimetry in the micro- to millisecond domain. For an ideal quantum yield of 100%, the enthalpy change, ΔH, coupled to the formation of the radical pair YZ⋅+QA− (where YZ is Tyr-161 of the D1 subunit of PSII) is estimated as −820 ± 250 meV. For a lower quantum yield of 70%, the enthalpy change is estimated to be −400 ± 250 meV. The observed nonthermal signal possibly is due to a contraction of the PSII protein volume (apparent ΔV of about −13 Å3). For the first time, the enthalpy change of the O2-evolving transition of the S-state cycle was monitored directly. Surprisingly, the reaction is only slightly exergonic. A value of ΔH(S3 ⇒ S0) of −210 meV is estimated, but also an enthalpy change of zero is within the error range. A prominent nonthermal photothermal beam deflection signal (apparent ΔV of about +42 Å3) may reflect O2 and proton release from the manganese complex, but also reorganization of the protein matrix. PMID:17993488

The artificial leaf.

PubMed

Nocera, Daniel G

2012-05-15

To convert the energy of sunlight into chemical energy, the leaf splits water via the photosynthetic process to produce molecular oxygen and hydrogen, which is in a form of separated protons and electrons. The primary steps of natural photosynthesis involve the absorption of sunlight and its conversion into spatially separated electron-hole pairs. The holes of this wireless current are captured by the oxygen evolving complex (OEC) of photosystem II (PSII) to oxidize water to oxygen. The electrons and protons produced as a byproduct of the OEC reaction are captured by ferrodoxin of photosystem I. With the aid of ferrodoxin-NADP(+) reductase, they are used to produce hydrogen in the form of NADPH. For a synthetic material to realize the solar energy conversion function of the leaf, the light-absorbing material must capture a solar photon to generate a wireless current that is harnessed by catalysts, which drive the four electron/hole fuel-forming water-splitting reaction under benign conditions and under 1 sun (100 mW/cm(2)) illumination. This Account describes the construction of an artificial leaf comprising earth-abundant elements by interfacing a triple junction, amorphous silicon photovoltaic with hydrogen- and oxygen-evolving catalysts made from a ternary alloy (NiMoZn) and a cobalt-phosphate cluster (Co-OEC), respectively. The latter captures the structural and functional attributes of the PSII-OEC. Similar to the PSII-OEC, the Co-OEC self-assembles upon oxidation of an earth-abundant metal ion from 2+ to 3+, may operate in natural water at room temperature, and is self-healing. The Co-OEC also activates H(2)O by a proton-coupled electron transfer mechanism in which the Co-OEC is increased by four hole equivalents akin to the S-state pumping of the Kok cycle of PSII. X-ray absorption spectroscopy studies have established that the Co-OEC is a structural relative of Mn(3)CaO(4)-Mn cubane of the PSII-OEC, where Co replaces Mn and the cubane is extended in a corner-sharing, head-to-tail dimer. The ability to perform the oxygen-evolving reaction in water at neutral or near-neutral conditions has several consequences for the construction of the artificial leaf. The NiMoZn alloy may be used in place of Pt to generate hydrogen. To stabilize silicon in water, its surface is coated with a conducting metal oxide onto which the Co-OEC may be deposited. The net result is that immersing a triple-junction Si wafer coated with NiMoZn and Co-OEC in water and holding it up to sunlight can effect direct solar energy conversion via water splitting. By constructing a simple, stand-alone device composed of earth-abundant materials, the artificial leaf provides a means for an inexpensive and highly distributed solar-to-fuels system that employs low-cost systems engineering and manufacturing. Through this type of system, solar energy can become a viable energy supply to those in the non-legacy world.

Synergistic effects of ultraviolet radiation, thermal cycling and atomic oxygen on altered and coated Kapton surfaces

NASA Technical Reports Server (NTRS)

Dever, Joyce A.; Bruckner, Eric J.; Rodriguez, Elvin

1992-01-01

The photovoltaic (PV) power system for Space Station Freedom (SSF) uses solar array blankets which provide structural support for the solar cells and house the electrical interconnections. In the low earth orbital (LEO) environment where SSF will be located, surfaces will be exposed to potentially damaging environmental conditions including solar ultraviolet (UV) radiation, thermal cycling, and atomic oxygen. It is necessary to use ground based tests to determine how these environmental conditions would affect the mass loss and optical properties of candidate SSF blanket materials. Silicone containing, silicone coated, and SiO(x) coated polyimide film materials were exposed to simulated LEO environmental conditions to determine their durability and whether the environmental conditions of UV, thermal cycling and oxygen atoms act synergistically on these materials. A candidate PV blanket material called AOR Kapton, a polysiloxane polyimide cast from a solution mixture, shows an improvement in durability to oxygen atoms erosion after exposure to UV radiation or thermal cycling combined with UV radiation. This may indicate that the environmental conditions react synergistically with this material, and the damage predicted by exposure to atomic oxygen alone is more severe than that which would occur in LEO where atomic oxygen, thermal cycling and UV radiation are present together.

A lithium–oxygen battery with a long cycle life in an air-like atmosphere

NASA Astrophysics Data System (ADS)

Asadi, Mohammad; Sayahpour, Baharak; Abbasi, Pedram; Ngo, Anh T.; Karis, Klas; Jokisaari, Jacob R.; Liu, Cong; Narayanan, Badri; Gerard, Marc; Yasaei, Poya; Hu, Xuan; Mukherjee, Arijita; Lau, Kah Chun; Assary, Rajeev S.; Khalili-Araghi, Fatemeh; Klie, Robert F.; Curtiss, Larry A.; Salehi-Khojin, Amin

2018-03-01

Lithium–air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium–oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium–oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium–air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium–oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

A lithium-oxygen battery with a long cycle life in an air-like atmosphere.

PubMed

Asadi, Mohammad; Sayahpour, Baharak; Abbasi, Pedram; Ngo, Anh T; Karis, Klas; Jokisaari, Jacob R; Liu, Cong; Narayanan, Badri; Gerard, Marc; Yasaei, Poya; Hu, Xuan; Mukherjee, Arijita; Lau, Kah Chun; Assary, Rajeev S; Khalili-Araghi, Fatemeh; Klie, Robert F; Curtiss, Larry A; Salehi-Khojin, Amin

2018-03-21

Lithium-air batteries are considered to be a potential alternative to lithium-ion batteries for transportation applications, owing to their high theoretical specific energy. So far, however, such systems have been largely restricted to pure oxygen environments (lithium-oxygen batteries) and have a limited cycle life owing to side reactions involving the cathode, anode and electrolyte. In the presence of nitrogen, carbon dioxide and water vapour, these side reactions can become even more complex. Moreover, because of the need to store oxygen, the volumetric energy densities of lithium-oxygen systems may be too small for practical applications. Here we report a system comprising a lithium carbonate-based protected anode, a molybdenum disulfide cathode and an ionic liquid/dimethyl sulfoxide electrolyte that operates as a lithium-air battery in a simulated air atmosphere with a long cycle life of up to 700 cycles. We perform computational studies to provide insight into the operation of the system in this environment. This demonstration of a lithium-oxygen battery with a long cycle life in an air-like atmosphere is an important step towards the development of this field beyond lithium-ion technology, with a possibility to obtain much higher specific energy densities than for conventional lithium-ion batteries.

Synergistic effects of ultraviolet radiation, thermal cycling, and atomic oxygen on altered and coated Kapton surfaces

NASA Technical Reports Server (NTRS)

Dever, Joyce A.; Bruckner, Eric J.; Rodriguez, Elvin

1992-01-01

The photovoltaic (PV) power system for Space Station Freedom (SSF) uses solar array blankets which provide structural support for the solar cells and house the electrical interconnections. In the low Earth orbital (LEO) environment where SSF will be located, surfaces will be exposed to potentially damaging environmental conditions including solar ultraviolet (UV) radiation, thermal cycling, and atomic oxygen. It is necessary to use ground based tests to determine how these environmental conditions would affect the mass loss and optical properties of candidate SSF blanket materials. Silicone containing, silicone coated, and SiO(x) coated polyimide film materials were exposed to simulated LEO environmental conditions to determine there durability and whether the environmental conditions of UV, thermal cycling and oxygen atoms act synergistically on these materials. A candidate PV blanket material called AOR Kapton, a polysiloxane polyimide cast from a solution mixture, shows an improvement in durability to oxygen atoms erosion after exposure to UV radiation or thermal cycling combined with UV radiation. This may indicate that the environmental conditions react synergistically with this material, and the damage predicted by exposure to atomic oxygen alone is more severe than that which would occur in LEO where atomic oxygen, thermal cycling and UV radiation are present together.

Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

PubMed Central

Guy, R. D.; Fogel, M. L.; Berry, J. A.

1993-01-01

Isotope discrimination during photosynthetic exchange of O2 and CO2 was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([delta], where 1 + [delta]/1000 equals the isotope effect, k16/k18 or k12/k13) was determined by analysis of residual substrate (O2 or CO2). The [delta] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per mille (thousand) sign]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per mille (thousand) sign] and independent of enzyme source, unlike carbon isotope discrimination: 30.3[per mille (thousand) sign] for spinach enzyme and 19.6 to 23[per mille (thousand) sign] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [delta] for O2 consumption catalyzed by glycolate oxidase was 22.7[per mille (thousand) sign]. The expected overall [delta] for photorespiration is about 21.7[per mille (thousand) sign]. Consistent with this, when Asparagus sprengeri Regel mesophyll cells approached the compensation point within a sealed vessel, the [delta]18O of dissolved O2 came to a steady-state value of about 21.5[per mille (thousand) sign] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global O cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. PMID:12231663

A stable organic-inorganic hybrid layer protected lithium metal anode for long-cycle lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinhui; Yang, Jun; Zhou, Jingjing; Zhang, Tao; Li, Lei; Wang, Jiulin; Nuli, Yanna

2017-10-01

A stable organic-inorganic hybrid layer (OIHL) is direct fabricated on lithium metal surface by the interfacial reaction of lithium metal foil with 1-chlorodecane and oxygen/carbon dioxide mixed gas. This favorable OIHL is approximately 30 μm thick and consists of lithium alkyl carbonate and lithium chloride. The lithium-oxygen batteries with OIHL protected lithium metal anode exhibit longer cycle life (340 cycles) than those with bare lithium metal anode (50 cycles). This desirable performance can be ascribed to the robust OIHL which prevents the growth of lithium dendrites and the corrosion of lithium metal.

Deoxygenation alters bacterial diversity and community composition in the ocean's largest oxygen minimum zone.

PubMed

Beman, J Michael; Carolan, Molly T

2013-01-01

Oceanic oxygen minimum zones (OMZs) have a central role in biogeochemical cycles and are expanding as a consequence of climate change, yet how deoxygenation will affect the microbial communities that control these cycles is unclear. Here we sample across dissolved oxygen gradients in the oceans' largest OMZ and show that bacterial richness displays a unimodal pattern with decreasing dissolved oxygen, reaching maximum values on the edge of the OMZ and decreasing within it. Rare groups on the OMZ margin are abundant at lower dissolved oxygen concentrations, including sulphur-cycling Chromatiales, for which 16S rRNA was amplified from extracted RNA. Microbial species distribution models accurately replicate community patterns based on multivariate environmental data, demonstrate likely changes in distributions and diversity in the eastern tropical North Pacific Ocean, and highlight the sensitivity of key bacterial groups to deoxygenation. Through these mechanisms, OMZ expansion may alter microbial composition, competition, diversity and function, all of which have implications for biogeochemical cycling in OMZs.

Deoxygenation alters bacterial diversity and community composition in the ocean’s largest oxygen minimum zone

NASA Astrophysics Data System (ADS)

Beman, J. Michael; Carolan, Molly T.

2013-10-01

Oceanic oxygen minimum zones (OMZs) have a central role in biogeochemical cycles and are expanding as a consequence of climate change, yet how deoxygenation will affect the microbial communities that control these cycles is unclear. Here we sample across dissolved oxygen gradients in the oceans’ largest OMZ and show that bacterial richness displays a unimodal pattern with decreasing dissolved oxygen, reaching maximum values on the edge of the OMZ and decreasing within it. Rare groups on the OMZ margin are abundant at lower dissolved oxygen concentrations, including sulphur-cycling Chromatiales, for which 16S rRNA was amplified from extracted RNA. Microbial species distribution models accurately replicate community patterns based on multivariate environmental data, demonstrate likely changes in distributions and diversity in the eastern tropical North Pacific Ocean, and highlight the sensitivity of key bacterial groups to deoxygenation. Through these mechanisms, OMZ expansion may alter microbial composition, competition, diversity and function, all of which have implications for biogeochemical cycling in OMZs.

Validation of a dual-cycle ergometer for exercise during 100 percent oxygen prebreathing

NASA Technical Reports Server (NTRS)

Wiegman, Janet F.; Ohlhausen, John H.; Webb, James T.; Pilmanis, Andrew A.

1992-01-01

A study has been designed to determine if exercise, while prebreathing 100 percent oxygen prior to decompression, can reduce the current resting-prebreathe time requirements for extravehicular activity and high altitude reconnaissance flight. For that study, a suitable exercise mode was required. Design considerations included space limitations, cost, pressure suit compatibility, ease and maintenance of calibration, accuracy of work output, and assurance that no significant mechanical advantage or disadvantage would be introduced into the system. In addition, the exercise device must enhance denitrogenation by incorporation of both upper and lower body musculature at high levels of oxygen consumption. The purpose of this paper is to describe the specially constructed, dual-cycle ergometer developed for simultaneous arm and leg exercise during prebreathing, and to compare maximal oxygen uptake obtained on the device to that obtained during leg-only cycle ergometry and treadmill testing. Results demonstrate the suitability of the dual-cycle ergometer as an appropriate tool for exercise research during 100 percent oxygen prebreathing.

The Oxygen Cycle.

ERIC Educational Resources Information Center

Swant, Gary D.

Produced for primary grades, this booklet provides study of the oxygen-carbon dioxide cycle in nature. Line drawings, a minimum amount of narrative, and a glossary of terms make up its content. The booklet is designed to be used as reading material, a coloring book, or for dramatic arts with students acting out parts of the cycle. This work was…

A Bifunctional Photosensitizer for Enhanced Fractional Photodynamic Therapy: Singlet Oxygen Generation in the Presence and Absence of Light.

PubMed

Turan, Ilke Simsek; Yildiz, Deniz; Turksoy, Abdurrahman; Gunaydin, Gurcan; Akkaya, Engin U

2016-02-18

The photosensitized generation of singlet oxygen within tumor tissues during photodynamic therapy (PDT) is self-limiting, as the already low oxygen concentrations within tumors is further diminished during the process. In certain applications, to minimize photoinduced hypoxia the light is introduced intermittently (fractional PDT) to allow time for the replenishment of cellular oxygen. This condition extends the time required for effective therapy. Herein, we demonstrated that a photosensitizer with an additional 2-pyridone module for trapping singlet oxygen would be useful in fractional PDT. Thus, in the light cycle, the endoperoxide of 2-pyridone is generated along with singlet oxygen. In the dark cycle, the endoperoxide undergoes thermal cycloreversion to produce singlet oxygen, regenerating the 2-pyridone module. As a result, the photodynamic process can continue in the dark as well as in the light cycles. Cell-culture studies validated this working principle in vitro. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How Life and Rocks Have Co-Evolved

NASA Astrophysics Data System (ADS)

Hazen, R.

2014-04-01

The near-surface environment of terrestrial planets and moons evolves as a consequence of selective physical, chemical, and biological processes - an evolution that is preserved in the mineralogical record. Mineral evolution begins with approximately 12 different refractory minerals that form in the cooling envelopes of exploding stars. Subsequent aqueous and thermal alteration of planetessimals results in the approximately 250 minerals now found in unweathered lunar and meteorite samples. Following Earth's accretion and differentiation, mineral evolution resulted from a sequence of geochemical and petrologic processes, which led to perhaps 1500 mineral species. According to some origin-of-life scenarios, a planet must progress through at least some of these stages of chemical processing as a prerequisite for life. Once life emerged, mineralogy and biology co-evolved and dramatically increased Earth's mineral diversity to >4000 species. Sequential stages of a planet's near-surface evolution arise from three primary mechanisms: (1) the progressive separation and concentration of the elements from their original relatively uniform distribution in the presolar nebula; (2) the increase in range of intensive variables such as pressure, temperature, and volatile activities; and (3) the generation of far-from-equilibrium conditions by living systems. Remote observations of the mineralogy of other terrestrial bodies may thus provide evidence for biological influences beyond Earth. Recent studies of mineral diversification through time reveal striking correlations with major geochemical, tectonic, and biological events, including large-changes in ocean chemistry, the supercontinent cycle, the increase of atmospheric oxygen, and the rise of the terrestrial biosphere.

40 CFR 60.144 - Test methods and procedures.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Emissions from Basic Oxygen Process Furnaces for Which Construction is Commenced After June 11, 1973 § 60... cycles. A cycle shall start at the beginning of either the scrap preheat or the oxygen blow and shall... number of primary oxygen blows. (3) Method 9 and the procedures in § 60.11 shall be used to determine...

40 CFR 60.144 - Test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Emissions from Basic Oxygen Process Furnaces for Which Construction is Commenced After June 11, 1973 § 60... cycles. A cycle shall start at the beginning of either the scrap preheat or the oxygen blow and shall... number of primary oxygen blows. (3) Method 9 and the procedures in § 60.11 shall be used to determine...

40 CFR 60.144 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Emissions from Basic Oxygen Process Furnaces for Which Construction is Commenced After June 11, 1973 § 60... cycles. A cycle shall start at the beginning of either the scrap preheat or the oxygen blow and shall... number of primary oxygen blows. (3) Method 9 and the procedures in § 60.11 shall be used to determine...

40 CFR 60.144 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Emissions from Basic Oxygen Process Furnaces for Which Construction is Commenced After June 11, 1973 § 60... cycles. A cycle shall start at the beginning of either the scrap preheat or the oxygen blow and shall... number of primary oxygen blows. (3) Method 9 and the procedures in § 60.11 shall be used to determine...

40 CFR 60.144 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Emissions from Basic Oxygen Process Furnaces for Which Construction is Commenced After June 11, 1973 § 60... cycles. A cycle shall start at the beginning of either the scrap preheat or the oxygen blow and shall... number of primary oxygen blows. (3) Method 9 and the procedures in § 60.11 shall be used to determine...

THE WATER-WATER CYCLE IN CHLOROPLASTS: Scavenging of Active Oxygens and Dissipation of Excess Photons.

PubMed

Asada, Kozi

1999-06-01

Photoreduction of dioxygen in photosystem I (PSI) of chloroplasts generates superoxide radicals as the primary product. In intact chloroplasts, the superoxide and the hydrogen peroxide produced via the disproportionation of superoxide are so rapidly scavenged at the site of their generation that the active oxygens do not inactivate the PSI complex, the stromal enzymes, or the scavenging system itself. The overall reaction for scavenging of active oxygens is the photoreduction of dioxygen to water via superoxide and hydrogen peroxide in PSI by the electrons derived from water in PSII, and the water-water cycle is proposed for these sequences. An overview is given of the molecular mechanism of the water-water cycle and microcompartmentalization of the enzymes participating in it. Whenever the water-water cycle operates properly for scavenging of active oxygens in chloroplasts, it also effectively dissipates excess excitation energy under environmental stress. The dual functions of the water-water cycle for protection from photoinihibition are discussed.

Nonequilibrium thermodynamics and maximum entropy production in the Earth system: applications and implications.

PubMed

Kleidon, Axel

2009-06-01

The Earth system is maintained in a unique state far from thermodynamic equilibrium, as, for instance, reflected in the high concentration of reactive oxygen in the atmosphere. The myriad of processes that transform energy, that result in the motion of mass in the atmosphere, in oceans, and on land, processes that drive the global water, carbon, and other biogeochemical cycles, all have in common that they are irreversible in their nature. Entropy production is a general consequence of these processes and measures their degree of irreversibility. The proposed principle of maximum entropy production (MEP) states that systems are driven to steady states in which they produce entropy at the maximum possible rate given the prevailing constraints. In this review, the basics of nonequilibrium thermodynamics are described, as well as how these apply to Earth system processes. Applications of the MEP principle are discussed, ranging from the strength of the atmospheric circulation, the hydrological cycle, and biogeochemical cycles to the role that life plays in these processes. Nonequilibrium thermodynamics and the MEP principle have potentially wide-ranging implications for our understanding of Earth system functioning, how it has evolved in the past, and why it is habitable. Entropy production allows us to quantify an objective direction of Earth system change (closer to vs further away from thermodynamic equilibrium, or, equivalently, towards a state of MEP). When a maximum in entropy production is reached, MEP implies that the Earth system reacts to perturbations primarily with negative feedbacks. In conclusion, this nonequilibrium thermodynamic view of the Earth system shows great promise to establish a holistic description of the Earth as one system. This perspective is likely to allow us to better understand and predict its function as one entity, how it has evolved in the past, and how it is modified by human activities in the future.

Biologically enhanced cathode design for improved capacity and cycle life for lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Oh, Dahyun; Qi, Jifa; Lu, Yi-Chun; Zhang, Yong; Shao-Horn, Yang; Belcher, Angela M.

2013-11-01

Lithium-oxygen batteries have a great potential to enhance the gravimetric energy density of fully packaged batteries by two to three times that of lithium ion cells. Recent studies have focused on finding stable electrolytes to address poor cycling capability and improve practical limitations of current lithium-oxygen batteries. In this study, the catalyst electrode, where discharge products are deposited and decomposed, was investigated as it has a critical role in the operation of rechargeable lithium-oxygen batteries. Here we report the electrode design principle to improve specific capacity and cycling performance of lithium-oxygen batteries by utilizing high-efficiency nanocatalysts assembled by M13 virus with earth-abundant elements such as manganese oxides. By incorporating only 3-5 wt% of palladium nanoparticles in the electrode, this hybrid nanocatalyst achieves 13,350 mAh g-1c (7,340 mAh g-1c+catalyst) of specific capacity at 0.4 A g-1c and a stable cycle life up to 50 cycles (4,000 mAh g-1c, 400 mAh g-1c+catalyst) at 1 A g-1c.

Highly active catalyst derived from a 3D foam of Fe(PO3)2/Ni2P for extremely efficient water oxidation

PubMed Central

Zhou, Haiqing; Yu, Fang; Sun, Jingying; He, Ran; Chen, Shuo; Chu, Ching-Wu; Ren, Zhifeng

2017-01-01

Commercial hydrogen production by electrocatalytic water splitting will benefit from the realization of more efficient and less expensive catalysts compared with noble metal catalysts, especially for the oxygen evolution reaction, which requires a current density of 500 mA/cm2 at an overpotential below 300 mV with long-term stability. Here we report a robust oxygen-evolving electrocatalyst consisting of ferrous metaphosphate on self-supported conductive nickel foam that is commercially available in large scale. We find that this catalyst, which may be associated with the in situ generated nickel–iron oxide/hydroxide and iron oxyhydroxide catalysts at the surface, yields current densities of 10 mA/cm2 at an overpotential of 177 mV, 500 mA/cm2 at only 265 mV, and 1,705 mA/cm2 at 300 mV, with high durability in alkaline electrolyte of 1 M KOH even after 10,000 cycles, representing activity enhancement by a factor of 49 in boosting water oxidation at 300 mV relative to the state-of-the-art IrO2 catalyst. PMID:28507120

Cyanobacteria HABs - Causes, Prevention, and Mitigation Workgroup Report.

USDA-ARS?s Scientific Manuscript database

Cyanobacteria (blue-green algae) are estimated to have evolved 3.5 billion years ago, at which time they began to add oxygen to the existing anaerobic atmosphere, actually changing the chemistry of the planet and allowing new life forms to evolve. These ubiquitous microbes are capable of tolerating ...

The Paleoproterozoic snowball Earth: a climate disaster triggered by the evolution of oxygenic photosynthesis.

PubMed

Kopp, Robert E; Kirschvink, Joseph L; Hilburn, Isaac A; Nash, Cody Z

2005-08-09

Although biomarker, trace element, and isotopic evidence have been used to claim that oxygenic photosynthesis evolved by 2.8 giga-annum before present (Ga) and perhaps as early as 3.7 Ga, a skeptical examination raises considerable doubt about the presence of oxygen producers at these times. Geological features suggestive of oxygen, such as red beds, lateritic paleosols, and the return of sedimentary sulfate deposits after a approximately 900-million year hiatus, occur shortly before the approximately 2.3-2.2 Ga Makganyene "snowball Earth" (global glaciation). The massive deposition of Mn, which has a high redox potential, practically requires the presence of environmental oxygen after the snowball. New age constraints from the Transvaal Supergroup of South Africa suggest that all three glaciations in the Huronian Supergroup of Canada predate the Snowball event. A simple cyanobacterial growth model incorporating the range of C, Fe, and P fluxes expected during a partial glaciation in an anoxic world with high-Fe oceans indicates that oxygenic photosynthesis could have destroyed a methane greenhouse and triggered a snowball event on time-scales as short as 1 million years. As the geological evidence requiring oxygen does not appear during the Pongola glaciation at 2.9 Ga or during the Huronian glaciations, we argue that oxygenic cyanobacteria evolved and radiated shortly before the Makganyene snowball.

Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake

PubMed Central

Walter, Xavier A.; Picazo, Antonio; Miracle, Maria R.; Vicente, Eduardo; Camacho, Antonio; Aragno, Michel; Zopfi, Jakob

2014-01-01

Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz. PMID:25538702

Removal of Ca 2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn 4O 5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

DOE PAGES

Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; ...

2015-05-19

We studied Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4O 5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1') and S 2 (S 2') states, the S 2'Y Z• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mnmore » K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z• (D1-Tyr161).« less

Removal of Ca(2+) from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study.

PubMed

Lohmiller, Thomas; Shelby, Megan L; Long, Xi; Yachandra, Vittal K; Yano, Junko

2015-10-29

Ca(2+)-depleted and Ca(2+)-reconstituted spinach photosystem II was studied using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca(2+) ion in the Mn4O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca(2+)-depleted S1 (S1') and S2 (S2') states, the S2'YZ(•) state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca(2+)-reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca(2+)-depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca(2+)-containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca(2+) ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca(2+) ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca(2+) removal are discussed, attributing to the Ca(2+) ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ(•) (D1-Tyr161).

Visible light induction of an electron paramagnetic resonance split signal in Photosystem II in the S(2) state reveals the importance of charges in the oxygen-evolving center during catalysis: a unifying model.

PubMed

Sjöholm, Johannes; Styring, Stenbjörn; Havelius, Kajsa G V; Ho, Felix M

2012-03-13

Cryogenic illumination of Photosystem II (PSII) can lead to the trapping of the metastable radical Y(Z)(•), the radical form of the redox-active tyrosine residue D1-Tyr161 (known as Y(Z)). Magnetic interaction between this radical and the CaMn(4) cluster of PSII gives rise to so-called split electron paramagnetic resonance (EPR) signals with characteristics that are dependent on the S state. We report here the observation and characterization of a split EPR signal that can be directly induced from PSII centers in the S(2) state through visible light illumination at 10 K. We further show that the induction of this split signal takes place via a Mn-centered mechanism, in the same way as when using near-infrared light illumination [Koulougliotis, D., et al. (2003) Biochemistry 42, 3045-3053]. On the basis of interpretations of these results, and in combination with literature data for other split signals induced under a variety of conditions (temperature and light quality), we propose a unified model for the mechanisms of split signal induction across the four S states (S(0), S(1), S(2), and S(3)). At the heart of this model is the stability or instability of the Y(Z)(•)(D1-His190)(+) pair that would be formed during cryogenic oxidation of Y(Z). Furthermore, the model is closely related to the sequence of transfers of protons and electrons from the CaMn(4) cluster during the S cycle and further demonstrates the utility of the split signals in probing the immediate environment of the oxygen-evolving center in PSII.

Convergence of QM/MM and Cluster Models for the Spectroscopic Properties of the Oxygen-Evolving Complex in Photosystem II.

PubMed

Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A

2013-08-13

The latest crystal structure of photosystem II at 1.9 Å resolution, which resolves the topology of the Mn4CaO5 oxygen evolving complex (OEC) at atomistic detail, enables a better correlation between structural features and spectroscopic properties than ever before. Building on the refined crystallographic model of the OEC and the protein, we present combined quantum mechanical/molecular mechanical (QM/MM) studies of the spectroscopic properties of the natural catalyst embedded in the protein matrix. Focusing on the S2 state of the catalytic cycle, we examine the convergence of not only structural parameters but also of the intracluster magnetic interactions in terms of exchange coupling constants and of experimentally relevant (55)Mn, (17)O, and (14)N hyperfine coupling constants with respect to QM/MM partitioning using five QM regions of increasing size. This enables us to assess the performance of the method and to probe second sphere effects by identifying amino acid residues that principally affect the spectroscopic properties of the OEC. Comparison between QM-only and QM/MM treatments reveals that whereas QM/MM models converge quickly to stable values, the QM cluster models need to incorporate significantly larger parts of the second coordination sphere and surrounding water molecules to achieve convergence for certain properties. This is mainly due to the sensitivity of the QM-only models to fluctuations in the hydrogen bonding network and ligand acidity. Additionally, a hydrogen bond that is typically omitted in QM-only treatments is shown to determine the hyperfine coupling tensor of the unique Mn(III) ion by regulating the rotation plane of the ligated D1-His332 imidazole ring, the only N-donor ligand of the OEC.

Quantum mechanics/molecular mechanics structural models of the oxygen-evolving complex of photosystem II.

PubMed

Sproviero, Eduardo M; Gascón, José A; McEvoy, James P; Brudvig, Gary W; Batista, Victor S

2007-04-01

The annual production of 260 Gtonnes of oxygen, during the process of photosynthesis, sustains life on earth. Oxygen is produced in the thylakoid membranes of green-plant chloroplasts and the internal membranes of cyanobacteria by photocatalytic water oxidation at the oxygen-evolving complex (OEC) of photosystem II (PSII). Recent breakthroughs in X-ray crystallography and advances in quantum mechanics/molecular mechanics (QM/MM) hybrid methods have enabled the construction of chemically sensible models of the OEC of PSII. The resulting computational structural models suggest the complete ligation of the catalytic center by amino acid residues, water, hydroxide and chloride, as determined from the intrinsic electronic properties of the oxomanganese core and the perturbational influence of the surrounding protein environment. These structures are found to be consistent with available mechanistic data, and are also compatible with X-ray diffraction models and extended X-ray absorption fine structure measurements. It is therefore conjectured that these OEC models are particularly relevant for the elucidation of the catalytic mechanism of water oxidation.

The evolution of the Krebs cycle: A promising subject for meaningful learning of biochemistry.

PubMed

da Costa, Caetano; Galembeck, Eduardo

2016-05-06

Evolution has been recognized as a key concept for biologists. To enhance comprehension and motivate biology undergraduates for the contents of central energetic metabolism, we addressed the Krebs cycle structure and functions in an evolutionary view. To this end, we created a study guide that contextualizes the emergence of the cyclic pathway, in light of the prokaryotic influence since the early anaerobic condition of the Earth to increase oxygen in the atmosphere. The study guide is composed of three interrelated sections: (1) a problem, designed to arouse curiosity, inform and motivate students, (2) a text about life evolution, including early microorganisms and the emergence of the Krebs cycle, and (3) questions for debate. The activity consisted on individual reading and peer discussion based on this written material, under the guidance of the instructors. The questions were designed to foster debate in an ever-increasing level of complexity and to strengthen the main contextual aspects leading to emergence, evolving, and permanency of a complex metabolic pathway. Based on classroom observation, analysis of student's written responses, and individual interviews, we noticed they were engaged and motivated by the task, especially during group discussion. The whole experience suggests that the study guide was a stimulus to broaden the comprehension of the Krebs cycle, reinforcing the evolutionary approach as an important subject for learning purposes. © 2016 by The International Union of Biochemistry and Molecular Biology, 44:288-296, 2016. © 2016 The International Union of Biochemistry and Molecular Biology.

Numerical simulations of the Cordilleran ice sheet through the last glacial cycle

NASA Astrophysics Data System (ADS)

Seguinot, Julien; Rogozhina, Irina; Stroeven, Arjen P.; Margold, Martin; Kleman, Johan

2016-03-01

After more than a century of geological research, the Cordilleran ice sheet of North America remains among the least understood in terms of its former extent, volume, and dynamics. Because of the mountainous topography on which the ice sheet formed, geological studies have often had only local or regional relevance and shown such a complexity that ice-sheet-wide spatial reconstructions of advance and retreat patterns are lacking. Here we use a numerical ice sheet model calibrated against field-based evidence to attempt a quantitative reconstruction of the Cordilleran ice sheet history through the last glacial cycle. A series of simulations is driven by time-dependent temperature offsets from six proxy records located around the globe. Although this approach reveals large variations in model response to evolving climate forcing, all simulations produce two major glaciations during marine oxygen isotope stages 4 (62.2-56.9 ka) and 2 (23.2-16.9 ka). The timing of glaciation is better reproduced using temperature reconstructions from Greenland and Antarctic ice cores than from regional oceanic sediment cores. During most of the last glacial cycle, the modelled ice cover is discontinuous and restricted to high mountain areas. However, widespread precipitation over the Skeena Mountains favours the persistence of a central ice dome throughout the glacial cycle. It acts as a nucleation centre before the Last Glacial Maximum and hosts the last remains of Cordilleran ice until the middle Holocene (6.7 ka).

Speculations on future opportunities to evolve Brayton powerplants aboard the space station

NASA Technical Reports Server (NTRS)

English, Robert E.

1987-01-01

The Space Station provides a unique, low-risk environment in which to evolve new capabilities. In this way, the Space Station will grow in capacity, in its range of capabilities, and its economy of operation as a laboratory and as a center for space operations. Although both Rankine and Brayton cycles, two concepts for solar dynamic power generation, now compete to power the station, this paper confines its attention to the Brayton cycle using a mixture of He and Xe as its working fluid. Such a Brayton powerplant to supply the station's increasing demands for both electric power and heat has the potential to gradually evolve higher and higher performance by exploiting already-evolved materials (ASTAR-811C and molten-Li heat storage), its peak cycle temperature rising ultimately to 1500 K. Adapting the station to exploit long tethers (200 to 300 km long) could yield increases in payloads to LEO, to GEO, and to distant destinations in the solar system. Such tethering of the Space Station would not only require additional power for electric propulsion but also would so increase nuclear safety that nuclear powerplants might provide this power. From an 8000-kWt SP-100 reactor, thermoelectric power generation could produce 300 kWe, or adapted solar-Brayton cycle, 2400 to 2800 kWe.

Liquefaction and Storage of In-Situ Oxygen on the Surface of Mars

NASA Technical Reports Server (NTRS)

Hauser, Daniel M.; Johnson, Wesley L.; Sutherlin, Steven G.

2016-01-01

ISRU is currently base-lined for the production of oxygen on the Martian surface in the Evolvable Mars Campaign Over 50 of return vehicle mass is oxygen for propulsion. There are two key cryogenic fluid-thermal technologies that need to be investigated to enable these architectures. High lift refrigeration systems. Thermal Insulation systems, either lightweight vacuum jackets of soft vacuum insulation systems.

Facile Method to Study Catalytic Oxygen Evolution Using a Dissolved Oxygen Optical Probe: An Undergraduate Chemistry Laboratory to Appreciate Artificial Photosynthesis

ERIC Educational Resources Information Center

Renderos, Genesis; Aquino, Tawanda; Gutierrez, Kristian; Badiei, Yosra M.

2017-01-01

Artificial photosynthesis (AP) is a synthetic chemical process that replicates natural photosynthesis to mass produce hydrogen as a clean fuel from sunlight-driven water splitting (2H[subscript 2]O [right arrow] O[subscript 2] + H[subscript 2]). In both natural and artificial photosynthesis, an oxygen-evolving catalyst (OEC) is needed to catalyze…

Cardiorespiratory demand of acute voluntary cycling with functional electrical stimulation in individuals with multiple sclerosis with severe mobility impairment.

PubMed

Edwards, Thomas; Motl, Robert W; Pilutti, Lara A

2018-01-01

Exercise training is one strategy for improving cardiorespiratory fitness (CRF) in multiple sclerosis (MS); however, few modalities are accessible for those with severe mobility impairment. Functional electrical stimulation (FES) cycling is an adapted exercise modality with the potential for improving CRF in people with severe MS. The objective of this study was to characterize the cardiorespiratory response of acute voluntary cycling with FES in people with MS with severe mobility impairment, and to compare this response to passive leg cycling. Eleven participants with MS that required assistance for ambulation completed a single bout of voluntary cycling with FES or passive leg cycling. Oxygen consumption, heart rate (HR), work rate (WR), and ratings of perceived exertion (RPE) were recorded throughout the session. For the FES group, mean exercising oxygen consumption was 8.7 ± 1.8 mL/(kg·min) -1 , or 63.5% of peak oxygen consumption. Mean HR was 102 ± 9.7 bpm, approximately 76.4% of peak HR. Mean WR was 27.0 ± 9.2 W, or 57.3% of peak WR, and median RPE was 13.5 (interquartile range = 5.5). Active cycling with FES was significantly (p < 0.05) more intense than passive leg cycling based on oxygen consumption, HR, WR, and RPE during exercise. In conclusion, voluntary cycling with FES elicited an acute response that corresponded with moderate-to vigorous-intensity activity, suggesting that active cycling with FES can elicit a sufficient stimulus for improving CRF.

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event.

PubMed

Luo, Genming; Junium, Christopher K; Izon, Gareth; Ono, Shuhei; Beukes, Nicolas J; Algeo, Thomas J; Cui, Ying; Xie, Shucheng; Summons, Roger E

2018-03-07

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte-Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.

A comparison of head motion and prefrontal haemodynamics during upright and recumbent cycling exercise.

PubMed

Tempest, Gavin D; Eston, Roger G; Parfitt, Gaynor

2017-11-01

The aim of this observational study was to compare head motion and prefrontal haemodynamics during exercise using three commercial cycling ergometers. Participants (n = 12) completed an incremental exercise test to exhaustion during upright, recumbent and semi-recumbent cycling. Head motion (using accelerometry), physiological data (oxygen uptake, end-tidal carbon dioxide [P ET CO 2 ] and heart rate) and changes in prefrontal haemodynamics (oxygenation, deoxygenation and blood volume using near infrared spectroscopy [NIRS]) were recorded. Despite no difference in oxygen uptake and heart rate, head motion was higher and P ET CO 2 was lower during upright cycling at maximal exercise (P<0·05). Analyses of covariance (covariates: head motion P>0·05; P ET CO 2 , P<0·01) revealed that prefrontal oxygenation was higher during semi-recumbent than recumbent cycling and deoxygenation and blood volume were higher during upright than recumbent and semi-recumbent cycling (respectively; P<0·05). This work highlights the robustness of the utility of NIRS to head motion and describes the potential postural effects upon the prefrontal haemodynamic response during upright and recumbent cycling exercise. © 2016 Scandinavian Society of Clinical Physiology and Nuclear Medicine. Published by John Wiley & Sons Ltd.

Tetrametallic molecular catalysts for photochemical water oxidation.

PubMed

Sartorel, Andrea; Bonchio, Marcella; Campagna, Sebastiano; Scandola, Franco

2013-03-21

Among molecular water oxidation catalysts (WOCs), those featuring a reactive set of four multi-redox transition metals can leverage an extraordinary interplay of electronic and structural properties. These are of particular interest, owing to their close structural, and possibly functional, relationship to the oxygen evolving complex of natural photosynthesis. In this review, special attention is given to two classes of tetrametallic molecular WOCs: (i) M(4)O(4) cubane-type structures stabilized by simple organic ligands, and (ii) systems in which a tetranuclear metal core is stabilized by coordination of two polyoxometalate (POM) ligands. Recent work in this rapidly evolving field is reviewed, with particular emphasis on photocatalytic aspects. Special attention is given to studies addressing the mechanistic complexity of these systems, sometimes overlooked in the rush for oxygen evolving performance. The complementary role of molecular WOCs and their relationship with bulk oxides and heterogeneous catalysis are discussed.

The evolution of photosynthesis...again?

PubMed

Rothschild, Lynn J

2008-08-27

'Replaying the tape' is an intriguing 'would it happen again?' exercise. With respect to broad evolutionary innovations, such as photosynthesis, the answers are central to our search for life elsewhere. Photosynthesis permits a large planetary biomass on Earth. Specifically, oxygenic photosynthesis has allowed an oxygenated atmosphere and the evolution of large metabolically demanding creatures, including ourselves. There are at least six prerequisites for the evolution of biological carbon fixation: a carbon-based life form; the presence of inorganic carbon; the availability of reductants; the presence of light; a light-harvesting mechanism to convert the light energy into chemical energy; and carboxylating enzymes. All were present on the early Earth. To provide the evolutionary pressure, organic carbon must be a scarce resource in contrast to inorganic carbon. The probability of evolving a carboxylase is approached by creating an inventory of carbon-fixation enzymes and comparing them, leading to the conclusion that carbon fixation in general is basic to life and has arisen multiple times. Certainly, the evolutionary pressure to evolve new pathways for carbon fixation would have been present early in evolution. From knowledge about planetary systems and extraterrestrial chemistry, if organic carbon-based life occurs elsewhere, photosynthesis -- although perhaps not oxygenic photosynthesis -- would also have evolved.

Augmented Oxygen-Dependent Killing of Leishmania.

DTIC Science & Technology

1992-06-30

reduction-oxidation cycling drugs: amphotericin B, menadione , and phenazine methosulfate. Promastigotes were exposed to the above drugs under...P02 = 2]..1 kPa) or hyperoxic conditions(P02 - 91.7 kPa). High oxygen tensions did not alter the lethal effects of either menadione or phenazine...effects of high oxygen tensions on the lethal effects of three reduction-oxidation cycling drugs: amphotericin B, menadione , and phenazine

BIODEGRADATION - MONITORED NATURAL ATTENUATION (MNA) FOR OXYGENATES: HOW IT EVOLVED, WHY IT OCCURS AND STABLE ISOTOPES

EPA Science Inventory

The organisms that degrade MtBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

Low-thrust chemical rocket engine study

NASA Technical Reports Server (NTRS)

Shoji, J. M.

1981-01-01

An analytical study evaluating thrust chamber cooling engine cycles and preliminary engine design for low thrust chemical rocket engines for orbit transfer vehicles is described. Oxygen/hydrogen, oxygen/methane, and oxygen/RP-1 engines with thrust levels from 444.8 N to 13345 N, and chamber pressures from 13.8 N/sq cm to 689.5 N/sq cm were evaluated. The physical and thermodynamic properties of the propellant theoretical performance data, and transport properties are documented. The thrust chamber cooling limits for regenerative/radiation and film/radiation cooling are defined and parametric heat transfer data presented. A conceptual evaluation of a number of engine cycles was performed and a 2224.1 N oxygen/hydrogen engine cycle configuration and a 2224.1 N oxygen/methane configuration chosen for preliminary engine design. Updated parametric engine data, engine design drawings, and an assessment of technology required are presented.

Evolving Oxygen Landscape of the Early Atmosphere and Oceans

NASA Astrophysics Data System (ADS)

Lyons, T. W.; Reinhard, C. T.; Planavsky, N. J.

2013-12-01

The past decade has witnessed remarkable advances in our understanding of oxygen on the early Earth, and a new framework, the topic of this presentation, is now in place to address the controls on spatiotemporal distributions of oxygen and their potential relationships to deep-Earth processes. Recent challenges to the Archean biomarker record have put an added burden on inorganic geochemistry to fingerprint and quantify the early production, accumulation, and variation of biospheric oxygen. Fortunately, a wide variety of techniques now point convincingly to photosynthetic oxygen production and dynamic accumulation well before the canonical Great Oxidation Event (GOE). Recent modeling of sulfur recycling over this interval allows for transient oxygen accumulation in the atmosphere without the disappearance of non-mass-dependent (NMD) sulfur isotope anomalies from the stratigraphic record and further allows for persistent accumulation in the atmosphere well before the permanent disappearance of NMD signals. This recent work suggests that the initial rise of oxygen may have occurred in fits and starts rather than a single step, and that once permanently present in the atmosphere, oxygen likely rose to high levels and then plummeted, in phase with the Paleoproterozoic Lomagundi positive carbon isotope excursion. More than a billion years of oxygen-free conditions in the deep ocean followed and set a challenging course for life, including limited abundances and diversity of eukaryotic organisms. Despite this widespread anoxia, sulfidic (euxinic) conditions were likely limited to productive ocean margins. Nevertheless, euxinia was sufficiently widespread to impact redox-dependent nutrient relationships, particularly the availability of bioessential trace metals critical in the nitrogen cycle, which spawned feedbacks that likely maintained oxygen at very low levels in the ocean and atmosphere and delayed the arrival of animals. Then, in the mid, pre-glacial Neoproterozoic we see evidence for an oxygenation event that significantly predated recent evidence for ocean ventilation in the post-glacial Ediacaran ocean. The trigger that facilitated the transition out of the oxygen-lean ';boring billion' is an area of active study. Additional evidence points to the likelihood of rising and falling oxygen levels through the later Neoproterozoic, which would have had a strong impact on early animal diversification and development of oxygen-demanding ecologies marked by large animals with complex trophic relationships. These observations now provide a context for interpreting the cause-and-effect relationships among the late Proterozoic rise in oxygen, the onset and dynamics of global-scale Neoproterozoic glaciation, metazoan diversification, and large-scale tectonic processes as surface expressions of deep-Earth processes.

The origin and evolution of oxygenic photosynthesis

NASA Technical Reports Server (NTRS)

Blankenship, R. E.; Hartman, H.

1998-01-01

The evolutionary developments that led to the ability of photosynthetic organisms to oxidize water to molecular oxygen are discussed. Two major changes from a more primitive non-oxygen-evolving reaction center are required: a charge-accumulating system and a reaction center pigment with a greater oxidizing potential. Intermediate stages are proposed in which hydrogen peroxide was oxidized by the reaction center, and an intermediate pigment, similar to chlorophyll d, was present.

LOX Tank Helium Removal for Propellant Scavenging

NASA Technical Reports Server (NTRS)

Chato, David J.

2009-01-01

System studies have shown a significant advantage to reusing the hydrogen and oxygen left in these tanks after landing on the Moon in fuel cells to generate power and water for surface systems. However in the current lander concepts, the helium used to pressurize the oxygen tank can substantially degrade fuel cell power and water output by covering the reacting surface with inert gas. This presentation documents an experimental investigation of methods to remove the helium pressurant while minimizing the amount of the oxygen lost. This investigation demonstrated that significant quantities of Helium (greater than 90% mole fraction) remain in the tank after draining. Although a single vent cycle reduced the helium quantity, large amounts of helium remained. Cyclic venting appeared to be more effective. Three vent cycles were sufficient to reduce the helium to small (less than 0.2%) quantities. Two vent cycles may be sufficient since once the tank has been brought up to pressure after the second vent cycle the helium concentration has been reduced to the less than 0.2% level. The re-pressurization process seemed to contribute to diluting helium. This is as expected since in order to raise the pressure liquid oxygen must be evaporated. Estimated liquid oxygen loss is on the order of 82 pounds (assuming the third vent cycle is not required).

Transcriptomic Analysis and Microscopic Observations in the Cyanobacterium UCYN-A during Diel Cycles

NASA Astrophysics Data System (ADS)

Muñoz-Marin, M. D. C.; Farnelid, H.; Zehr, J. P.

2016-02-01

Candidatus Atelocyanobacterium thalassa (UCYN-A) is a nitrogen-fixing marine cyanobacterium recently recognized for its widespread distribution and significant contributions to oceanic nitrogen (N2)-fixation. UCYN-A is a group of related cyanobacteria that are symbiotic with a single-celled eukaryotic phytoplankter, the haptophyte Braarudosphaera bigelowii. UCYN-A fixes N2 and expresses nitrogenase during the day. Since the nitrogenase is inactivated by oxygen evolved through photosynthesis, most cyanobacteria use temporal or spatial separation of photosynthesis and N2 fixation. Genomic studies revealed that UCYN-A lacks the entire PSII apparatus (photosystem II). The lack of oxygenic photosynthesis at least partially explains why they can fix nitrogen during the day, although the host is a photoautotroph. However, UCYN-A has retained photosystem I (PSI), and PSI activity may be important in the energetics of N2 fixation in the symbiosis. Because UCYN-A lacks photosystem II, which normally supplies electrons to photosystem I from water, UCYN-A needs alternative electron donors if it uses photosystem I to make the reductant NADPH. In order to determine if UCYN-A expresses photosynthetic genes and which other proteins may be involved with energy metabolism, we developed a whole genome array to examine gene transcription over the diel cycle in two strains. Our results show that there is a temporal separation of the expression of photosynthesis genes from the expression of nitrogenase genes. Moreover, the transcription profile of NADH dehydrogenases and hydrogenases suggest they may be involved as alternative electron donors for the N2 fixation. In addition, we used a double-CARD-FISH (Catalyzed Reporter Deposition-Fluorescence in situ Hybridization) assay to study cell division of the host and symbiont during diel cycles in relation to UCYN-A gene expression carried out during the transcriptomic analysis. These results help us move toward a deeper understanding of the metabolism of this unusual cyanobacterium and the differences in environmental adaptations between these two strains.

What can we infer about the origin of sex in early eukaryotes?

PubMed Central

2016-01-01

Current analysis shows that the last eukaryotic common ancestor (LECA) was capable of full meiotic sex. The original eukaryotic life cycle can probably be described as clonal, interrupted by episodic sex triggered by external or internal stressors. The cycle could have started in a highly flexible form, with the interruption of either diploid or haploid clonal growth determined by stress signals only. Eukaryotic sex most likely evolved in response to a high mutation rate, arising from the uptake of the endosymbiont, as this (proto) mitochondrion generated internal reactive oxygen species. This is consistent with the likely development of full meiotic sex from a diverse set of existing archaeal (the host of the endosymbiont) repair and signalling mechanisms. Meiotic sex could thus have been one of the fruits of symbiogenesis at the basis of eukaryotic origins: a product of the merger by which eukaryotic cells arose. Symbiogenesis also explains the large-scale migration of organellar DNA to the nucleus. I also discuss aspects of uniparental mitochondrial inheritance and mitonuclear interactions in the light of the previous analysis. This article is part of the themed issue ‘Weird sex: the underappreciated diversity of sexual reproduction’. PMID:27619694

What can we infer about the origin of sex in early eukaryotes?

PubMed

Speijer, Dave

2016-10-19

Current analysis shows that the last eukaryotic common ancestor (LECA) was capable of full meiotic sex. The original eukaryotic life cycle can probably be described as clonal, interrupted by episodic sex triggered by external or internal stressors. The cycle could have started in a highly flexible form, with the interruption of either diploid or haploid clonal growth determined by stress signals only. Eukaryotic sex most likely evolved in response to a high mutation rate, arising from the uptake of the endosymbiont, as this (proto) mitochondrion generated internal reactive oxygen species. This is consistent with the likely development of full meiotic sex from a diverse set of existing archaeal (the host of the endosymbiont) repair and signalling mechanisms. Meiotic sex could thus have been one of the fruits of symbiogenesis at the basis of eukaryotic origins: a product of the merger by which eukaryotic cells arose. Symbiogenesis also explains the large-scale migration of organellar DNA to the nucleus. I also discuss aspects of uniparental mitochondrial inheritance and mitonuclear interactions in the light of the previous analysis.This article is part of the themed issue 'Weird sex: the underappreciated diversity of sexual reproduction'. © 2016 The Author(s).

Protein Ligation of the Photosynthetic Oxygen-Evolving Center

PubMed Central

Debus, Richard J.

2008-01-01

Photosynthetic water oxidation is catalyzed by a unique Mn4Ca cluster in Photosystem II. The ligation environment of the Mn4Ca cluster optimizes the cluster’s reactivity at each step in the catalytic cycle and minimizes the release of toxic, partly oxidized intermediates. However, our understanding of the cluster’s ligation environment remains incomplete. Although the recent X-ray crystallographic structural models have provided great insight and are consistent with most conclusions of earlier site-directed mutagenesis studies, the ligation environments of the Mn4Ca cluster in the two available structural models differ in important respects. Furthermore, while these structural models and the earlier mutagenesis studies agree on the identity of most of the Mn4Ca cluster’s amino acid ligands, they disagree on the identity of others. This review describes mutant characterizations that have been undertaken to probe the ligation environment of the Mn4Ca cluster, some of which have been inspired by the recent X-ray crystallographic structural models. Many of these characterizations have involved Fourier Transform Infrared (FTIR) difference spectroscopy because of the extreme sensitivity of this form of spectroscopy to the dynamic structural changes that occur during an enzyme’s catalytic cycle. PMID:18496594

Nano-engineered intrapores in nanoparticles of PtNi networks for increased oxygen reduction reaction activity

NASA Astrophysics Data System (ADS)

Ding, Jieting; Ji, Shan; Wang, Hui; Key, Julian; Brett, Dan J. L.; Wang, Rongfang

2018-01-01

Network-like metallic alloys of solid nanoparticles have been frequently reported as promising electrocatalysts for fuel cells. The three-dimensional structure of such networks is rich in pores in the form of voids between nanoparticles, which collectively expose a large surface area for catalytic activity. Herein, we present a novel solution to this problem using a precursor comprising a flocculent core-shell PtNi@Ni to produce PtNi network catalysts with nanoparticle intraporosity after carefully controlled electrochemical dealloying. Physical characterization shows a hierarchical level of nanoporosity (intrapores within nanoparticles and pores between them) evolves during the controlled electrochemical dealloying, and that a Pt-rich surface also forms after 22 cycles of Ni leaching. In ORR cycling, the PtNi networks gain 4-fold activity in both jECSA and jmass over a state of the art Pt/C electrocatalyst, and also significantly exceed previously reported PtNi networks. In ORR degradation tests, the PtNi networks also proved stable, dropping by 30.4% and 62.6% in jECSA and jmass respectively. The enhanced performance of the catalyst is evident, and we also propose that the presented synthesis procedure can be generally applied to developing other metallic networks.

Effects of Surface Oxygen on the Performance of Carbon as an Anode in Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Clark, Gregory W.

2001-01-01

Carbon materials with similar bulk structure but different surface oxygen were compared for their performance as anodes in lithium-ion battery. The bulk structure was such that the graphene planes were perpendicular to the surface. Three types of surfaces were examined: surface containing C=O type oxygen. surface containing -O-C type oxygen, and surface containing high concentration of active sites. The test involved cycles of lithium insertion into and release from the carbon materials, which was in the half cells of carbon/saturated LiI-50/50 (vol %) EC and DMC/lithium. During the first cycle of lithium insertion, the presence of adsorbed oxygen, -O-C type oxygen, active carbon sites, and C=O type oxygen resulted in the formation of solid-electrolyte interface (SEI) when the carbon's voltage relative to lithium metal was >1.35, 1 to 1.35, 0.5 to 1, and 0.67 to 0.7 V, respectively. An optimum -O-C type oxygen and a minimum C=O type oxygen was found to increase the reversible and decrease the irreversible capacity of carbon. Active sites on the carbon surface result in a large irreversible capacity and a second lithium insertion-release mechanism. However, this new mechanism has a short cycle life.

MODELING NITROGEN-CARBON CYCLING AND OXYGEN CONSUMPTION IN BOTTOM SEDIMENTS

EPA Science Inventory

A model framework is presented for simulating nitrogen and carbon cycling at the sediment–water interface, and predicting oxygen consumption by oxidation reactions inside the sediments. Based on conservation of mass and invoking simplifying assumptions, a coupled system of diffus...

Molecular Evolution of the Oxygen-Binding Hemerythrin Domain

PubMed Central

Alvarez-Carreño, Claudia; Becerra, Arturo; Lazcano, Antonio

2016-01-01

Background The evolution of oxygenic photosynthesis during Precambrian times entailed the diversification of strategies minimizing reactive oxygen species-associated damage. Four families of oxygen-carrier proteins (hemoglobin, hemerythrin and the two non-homologous families of arthropodan and molluscan hemocyanins) are known to have evolved independently the capacity to bind oxygen reversibly, providing cells with strategies to cope with the evolutionary pressure of oxygen accumulation. Oxygen-binding hemerythrin was first studied in marine invertebrates but further research has made it clear that it is present in the three domains of life, strongly suggesting that its origin predated the emergence of eukaryotes. Results Oxygen-binding hemerythrins are a monophyletic sub-group of the hemerythrin/HHE (histidine, histidine, glutamic acid) cation-binding domain. Oxygen-binding hemerythrin homologs were unambiguously identified in 367/2236 bacterial, 21/150 archaeal and 4/135 eukaryotic genomes. Overall, oxygen-binding hemerythrin homologues were found in the same proportion as single-domain and as long protein sequences. The associated functions of protein domains in long hemerythrin sequences can be classified in three major groups: signal transduction, phosphorelay response regulation, and protein binding. This suggests that in many organisms the reversible oxygen-binding capacity was incorporated in signaling pathways. A maximum-likelihood tree of oxygen-binding hemerythrin homologues revealed a complex evolutionary history in which lateral gene transfer, duplications and gene losses appear to have played an important role. Conclusions Hemerythrin is an ancient protein domain with a complex evolutionary history. The distinctive iron-binding coordination site of oxygen-binding hemerythrins evolved first in prokaryotes, very likely prior to the divergence of Firmicutes and Proteobacteria, and spread into many bacterial, archaeal and eukaryotic species. The later evolution of the oxygen-binding hemerythrin domain in both prokaryotes and eukaryotes led to a wide variety of functions, ranging from protection against oxidative damage in anaerobic and microaerophilic organisms, to oxygen supplying to particular enzymes and pathways in aerobic and facultative species. PMID:27336621

LEO-to-GEO low thrust chemical propulsion

NASA Technical Reports Server (NTRS)

Shoji, J. M.

1980-01-01

One approach being considered for transporting large space structures from low Earth orbit (LEO) to geosynchronous equatorial orbit (GEO) is the use of low thrust chemical propulsion systems. A variety of chemical rocket engine cycles evaluated for this application for oxygen/hydrogen and oxygen/hydrocarbon propellants (oxygen/methane and oxygen/RF-1) are discussed. These cycles include conventional propellant turbine drives, turboalternator/electric motor pump drive, and fuel cell/electric motor pump drive as well as pressure fed engines. Thrust chamber cooling analysis results are presented for regenerative/radiation and film/radiation cooling.

Isolation Of PS II Nanoparticles And Oxygen Evolution Studies In Synechococcus Spp. PCC 7942 Under Heavy Metal Stress

NASA Astrophysics Data System (ADS)

Ahmad, Iffat Zareen; Sundaram, Shanthy; Tripathi, Ashutosh; Soumya, K. K.

2009-06-01

The effect of heavy metals was seen on the oxygen evolution pattern of a unicellular, non-heterocystous cyanobacterial strain of Synechococcus spp. PCC 7942. It was grown in a BG-11 medium supplemented with heavy metals, namely, nickel, copper, cadmium and mercury. Final concentrations of the heavy metal solution used in the culture were 0.1, 0.4 and 1 μM. All the experiments were performed in the exponential phase of the culture. Oxygen-evolving photosystem II (PS II) particles were purified from Synechococcus spp. PCC 7942 by a single-step Ni2+-affinity column chromatography after solubilization of thylakoid membranes with sucrose monolaurate. Oxygen evolution was measured with Clark type oxygen electrode fitted with a circulating water jacket. The light on the surface of the vessel was 10 w/m2. The cultures were incubated in light for 15 minutes prior to the measurement of oxygen evolution. Oxygen evolution was measured in assay mixture containing phosphate buffer (pH-7.5, 0.1 M) in the presence of potassium ferricyanide as the electron acceptor. The preparation from the control showed a high oxygen-evolving activity of 2, 300-2, 500 pmol O2 (mg Chl)-1 h-1 while the activity was decreased in the cultures grown with heavy metals. The inhibition of oxygen evolution shown by the organism in the presence of different metals was in the order Hg>Ni>Cd>Cu. Such heavy metal resistant strains will find application in the construction of PS II- based biosensors for the monitoring of pollutants.

Reversible Oxygenation of 2,4-Diaminobutanoic Acid-Co(II) Complexes

PubMed Central

Li, Hui; Yue, Fan; Wen, Hongmei

2016-01-01

This paper introduces the structural characterization and studies on reversible oxygenation behavior of a new oxygen carrier Co(II)-2,4-diaminobutanoic acid (DABA) complex in aqueous solution. The composition of the oxygenated complex was determined by gas volumetric method, molar ratio method, and mass spectrometry, and the formula of the oxygenated complex was determined to be [Co(DABA)2O2]. In aqueous solution, the complex can continuously uptake and release dioxygen and exhibit excellent reversibility of oxygenation and deoxygenation ability. This complex can maintain 50% of its original oxygenation capacity after 30 cycles in 24 h and retain 5% of the original oxygenation capacity after more than 260 cycles after 72 h. When a ligand analogue was linked to histidine (His), the new complex exhibited as excellent reversible oxygenation property as His-Co(II) complex. Insight into the relationship between structural detail and oxygenation properties will provide valuable suggestion for a new family of oxygen carriers. PMID:27648004

MNA of Chlorinated Solvents and Fuel Oxygenates: Why it occurs, how it evolved, and using stable carbon isotopes to predict plume behavior

EPA Science Inventory

The organisms that degrade MTBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

NASA Astrophysics Data System (ADS)

Young, M. B.; Kendall, C.; Paytan, A.

2013-12-01

The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and controls on biological cycling within hydrologic systems.

Oxygen dynamics in photosynthetic membranes.

NASA Astrophysics Data System (ADS)

Savikhin, Sergei; Kihara, Shigeharu

2008-03-01

Production of oxygen by oxygenic photosynthetic organisms is expected to raise oxygen concentration within their photosynthetic membranes above normal aerobic values. These raised levels of oxygen may affect function of many proteins within photosynthetic cells. However, experiments on proteins in vitro are usually performed in aerobic (or anaerobic) conditions since the oxygen content of a membrane is not known. Using theory of diffusion and measured oxygen production rates we estimated the excess levels of oxygen in functioning photosynthetic cells. We show that for an individual photosynthetic cell suspended in water oxygen level is essentially the same as that for a non-photosynthetic sell. These data suggest that oxygen protection mechanisms may have evolved after the development of oxygenic photosynthesis in primitive bacteria and was driven by the overall rise of oxygen concentration in the atmosphere. Substantially higher levels of oxygen are estimated to occur in closely packed colonies of photosynthetic bacteria and in green leafs.

The evolution of glutathione metabolism in phototrophic microorganisms

NASA Technical Reports Server (NTRS)

Fahey, R. C.; Buschbacher, R. M.; Newton, G. L.

1987-01-01

Of the many roles ascribed to glutathione (GSH) the one most clearly established is its role in the protection of higher eucaryotes against oxygen toxicity through destruction of thiol-reactive oxygen byproducts. If this is the primary function of GSH then GSH metabolism should have evolved during or after the evolution of oxygenic photosynthesis. That many bacteria do not produce GSH is consistent with this view. In the present study we have examined the low-molecular-weight thiol composition of a variety of phototrophic microorganisms to ascertain how evolution of GSH production is related to evolution of oxygenic photosynthesis. Cells were extracted in the presence of monobromobimane (mBBr) to convert thiols to fluorescent derivatives, which were analyzed by high-pressure liquid chromatography. Significant levels of GSH were not found in the green bacteria (Chlorobium thiosulfatophilum and Chloroflexus aurantiacus). Substantial levels of GSH were present in the purple bacteria (Chromatium vinosum, Rhodospirillum rubrum, Rhodobacter sphaeroides, and Rhodocyclus gelatinosa), the cyanobacteria [Anacystis nidulans, Microcoleus chthonoplastes S.G., Nostoc muscorum, Oscillatoria amphigranulata, Oscillatoria limnetica, Oscillatoria sp. (Stinky Spring, Utah), Oscillatoria terebriformis, Plectonema boryanum, and Synechococcus lividus], and eucaryotic algae (Chlorella pyrenoidsa, Chlorella vulgaris, Euglena gracilis, Scenedesmus obliquus, and Chlamydomonas reinhardtii). Other thiols measured included cysteine, gamma-glutamylcysteine, thiosulfate, coenzyme A, and sulfide; several unidentified thiols were also detected. Many of the organisms examined also exhibited a marked ability to reduce mBBr to syn-(methyl,methyl)bimane, an ability that was quenched by treatment with 2-pyridyl disulfide or 5,5'-bisdithio-(2-nitrobenzoic acid) prior to reaction with mBBr. These observations indicate the presence of a reducing system capable of electron transfer to mBBr and reduction of reactive disulfides. The distribution of GSH in phototrophic eubacteria indicates that GSH synthesis evolved at or around the time that oxygenic photosynthesis evolved.

Crystallization of Photosystem II for Time-Resolved Structural Studies Using an X-ray Free Electron Laser

PubMed Central

Coe, Jesse; Kupitz, Christopher; Basu, Shibom; Conrad, Chelsie E.; Roy-Chowdhury, Shatabdi; Fromme, Raimund; Fromme, Petra

2015-01-01

Photosystem II (PSII) is a membrane protein supercomplex that executes the initial reaction of photosynthesis in higher plants, algae, and cyanobacteria. It captures the light from the sun to catalyze a transmembrane charge separation. In a series of four charge separation events, utilizing the energy from four photons, PSII oxidizes two water molecules to obtain dioxygen, four protons, and four electrons. The light reactions of photosystems I and II (PSI and PSII) result in the formation of an electrochemical transmembrane proton gradient that is used for the production of ATP. Electrons that are subsequently transferred from PSI via the soluble protein ferredoxin to ferredoxin-NADP+ reductase that reduces NADP+ to NADPH. The products of photosynthesis and the elemental oxygen evolved sustain all higher life on Earth. All oxygen in the atmosphere is produced by the oxygen-evolving complex in PSII, a process that changed our planet from an anoxygenic to an oxygenic atmosphere 2.5 billion years ago. In this chapter, we provide recent insight into the mechanisms of this process and methods used in probing this question. PMID:25950978

Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.

PubMed

Vaddypally, Shivaiah; Kondaveeti, Sandeep K; Karki, Santosh; Van Vliet, Megan M; Levis, Robert J; Zdilla, Michael J

2017-04-05

The molecular mechanism of the Oxygen Evolving Center of photosystem II has been under debate for decades. One frequently cited proposal is the nucleophilic attack by water hydroxide on a pendant Mn═O moiety, though no chemical example of this reactivity at a manganese cubane cluster has been reported. We describe here the preparation, characterization, and a reactivity study of a synthetic manganese cubane cluster with a pendant manganese-oxo moiety. Reaction of this cluster with alkenes results in oxygen and hydrogen atom transfer reactions to form alcohol- and ketone-based oxygen-containing products. Nitrene transfer from core imides is negligible. The inorganic product is a cluster identical to the precursor, but with the pendant Mn═O moiety replaced by a hydrogen abstracted from the organic substrate, and is isolated in quantitative yield. 18 O and 2 H isotopic labeling studies confirm the transfer of atoms between the cluster and the organic substrate. The results suggest that the core cubane structure of this model compound remains intact, and that the pendant Mn═O moiety is preferentially reactive.

Integrated Heat Switch/Oxide Sorption Compressor

NASA Technical Reports Server (NTRS)

Bard, Steven

1989-01-01

Thermally-driven, nonmechanical compressor uses container filled with compressed praseodymium cerium oxide powder (PrCeOx) to provide high-pressure flow of oxygen gas for driving closed-cycle Joule-Thomson-expansion refrigeration unit. Integrated heat switch/oxide sorption compressor has no moving parts except check valves, which control flow of oxygen gas between compressor and closed-cycle Joule-Thomson refrigeration system. Oxygen expelled from sorbent at high pressure by evacuating heat-switch gap and turning on heater.

Intermediates of Krebs cycle correct the depression of the whole body oxygen consumption and lethal cooling in barbiturate poisoning in rat.

PubMed

Ivnitsky, Jury Ju; Schäfer, Timur V; Malakhovsky, Vladimir N; Rejniuk, Vladimir L

2004-10-01

Rats poisoned with one LD50 of thiopental or amytal are shown to increase oxygen consumption when intraperitoneally given sucinate, malate, citrate, alpha-ketoglutarate, dimethylsuccinate or glutamate (the Krebs cycle intermediates or their precursors) but not when given glucose, pyruvate, acetate, benzoate or nicotinate (energy substrates of other metabolic stages etc). Survival was increased with succinate or malate from control groups, which ranged from 30-83% to 87-100%. These effects were unrelated to respiratory depression or hypoxia as judged by little or no effect of succinate on ventilation indices and by the lack of effect of oxygen administration. Body cooling of comatose rats at ambient temperature approximately 19 degrees C became slower with succinate, the rate of cooling correlated well with oxygen consumption decrease. Succinate had no potency to modify oxygen consumption and body temperature in intact rats. A condition for antidote effect of the Krebs intermediate was sufficiently high dosage (5 mmol/kg), further dose increase made no odds. Repeated dosing of succinate had more marked protective effect, than a single one, to oxygen consumption and tended to promote the attenuation of lethal effect of barbiturates. These data suggest that suppression of whole body oxygen consumption with barbiturate overdose could be an important contributor to both body cooling and mortality. Intermediates of Krebs cycle, not only succinate, may have a pronounced therapeutic effect under the proper treatment regimen. Availability of Krebs cycle intermediates may be a limiting factor for the whole body oxygen consumption in barbiturate coma, its role in brain needs further elucidation.

Flammability and sensitivity of materials in oxygen-enriched atmospheres; Proceedings of the Fourth International Symposium, Las Cruces, NM, Apr. 11-13, 1989. Volume 4

NASA Technical Reports Server (NTRS)

Stoltzfus, Joel M. (Editor); Benz, Frank J. (Editor); Stradling, Jack S. (Editor)

1989-01-01

The present volume discusses the ignition of nonmetallic materials by the impact of high-pressure oxygen, the promoted combustion of nine structural metals in high-pressure gaseous oxygen, the oxygen sensitivity/compatibility ranking of several materials by different test methods, the ignition behavior of silicon greases in oxygen atmospheres, fire spread rates along cylindrical metal rods in high-pressure oxygen, and the design of an ignition-resistant, high pressure/temperature oxygen valve. Also discussed are the promoted ignition of oxygen regulators, the ignition of PTFE-lined flexible hoses by rapid pressurization with oxygen, evolving nonswelling elastomers for high-pressure oxygen environments, the evaluation of systems for oxygen service through the use of the quantitative fault-tree analysis, and oxygen-enriched fires during surgery of the head and neck.

Impact of variability in coastal fog on photosynthesis and dissolved oxygen levels in shallow water habitats: Salmon Creek estuary case study

NASA Astrophysics Data System (ADS)

Largier, J. L.

2013-12-01

Coastal fog reduces available light levels that in turn reduce rates of photosynthesis and oxygen production. This effect can be seen in perturbations of the day-night production-respiration cycle that leads to increase and decrease in dissolved oxygen in shallow-water habitats. In well stratified coastal lagoons, a lower layer may be isolated from the atmosphere so that small changes in photosynthetically active radiation (PAR) are evident in perturbations of the typical day-night cycle of oxygen concentration. This effect is observed in the summertime, mouth-closed Salmon Creek Estuary, located in Sonoma County (California). Sub-diurnal fluctuations in dissolved oxygen in Salmon Creek Estuary correlate with deviations from the clear-sky diurnal cycle in PAR. Similar effects are observed in other estuaries and the process by which fog controls photosynthesis can be expected to occur throughout coastal California, although the effect may not be easily observable in data collected from open waters where mixing and bloom dynamics are likely to dominate temporal variability in biogenic properties like dissolved oxygen.

Characterization and modeling of SET/RESET cycling induced read-disturb failure time degradation in a resistive switching memory

NASA Astrophysics Data System (ADS)

Su, Po-Cheng; Hsu, Chun-Chi; Du, Sin-I.; Wang, Tahui

2017-12-01

Read operation induced disturbance in SET-state in a tungsten oxide resistive switching memory is investigated. We observe that the reduction of oxygen vacancy density during read-disturb follows power-law dependence on cumulative read-disturb time. Our study shows that the SET-state read-disturb immunity progressively degrades by orders of magnitude as SET/RESET cycle number increases. To explore the cause of the read-disturb degradation, we perform a constant voltage stress to emulate high-field stress effects in SET/RESET cycling. We find that the read-disturb failure time degradation is attributed to high-field stress-generated oxide traps. Since the stress-generated traps may substitute for some of oxygen vacancies in forming conductive percolation paths in a switching dielectric, a stressed cell has a reduced oxygen vacancy density in SET-state, which in turn results in a shorter read-disturb failure time. We develop an analytical read-disturb degradation model including both cycling induced oxide trap creation and read-disturb induced oxygen vacancy reduction. Our model can well reproduce the measured read-disturb failure time degradation in a cycled cell without using fitting parameters.

Orientation of Calcium in the Mn4Ca Cluster of the Oxygen-Evolving Complex Determined Using Polarized Strontium EXAFS of Photosystem II Membranes†

PubMed Central

Cinco, Roehl M.; Robblee, John H.; Messinger, Johannes; Fernandez, Carmen; Holman, Karen L. McFarlane; Sauer, Kenneth; Yachandra, Vittal K.

2014-01-01

The oxygen-evolving complex of photosystem II (PS II) in green plants and algae contains a cluster of four Mn atoms in the active site, which catalyzes the photoinduced oxidation of water to dioxygen. Along with Mn, calcium and chloride ions are necessary cofactors for proper functioning of the complex. The current study using polarized Sr EXAFS on oriented Sr-reactivated samples shows that Fourier peak II, which fits best to Mn at 3.5 Å rather than lighter atoms (C, N, O, or Cl), is dichroic, with a larger magnitude at 10° (angle between the PS II membrane normal and the X-ray electric field vector) and a smaller magnitude at 80°. Analysis of the dichroism of the Sr EXAFS yields a lower and upper limit of 0° and 23° for the average angle between the Sr–Mn vectors and the membrane normal and an isotropic coordination number (number of Mn neighbors to Sr) of 1 or 2 for these layered PS II samples. The results confirm the contention that Ca (Sr) is proximal to the Mn cluster and lead to refined working models of the heteronuclear Mn4Ca cluster of the oxygen-evolving complex in PS II. PMID:15491134

A Discussion of Oxygen Recovery Definitions and Key Performance Parameters for Closed-Loop Atmosphere Revitalization Life Support Technology Development

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Perry, Jay L.

2016-01-01

Over the last 55 years, NASA has evolved life support for crewed space exploration vehicles from simple resupply during Project Mercury to the complex and highly integrated system of systems aboard the International Space Station. As NASA targets exploration destinations farther from low Earth orbit and mission durations of 500 to 1000 days, life support systems must evolve to meet new requirements. In addition to having more robust, reliable, and maintainable hardware, limiting resupply becomes critical for managing mission logistics and cost. Supplying a crew with the basics of food, water, and oxygen become more challenging as the destination ventures further from Earth. Aboard ISS the Atmosphere Revitalization Subsystem (ARS) supplies the crew's oxygen demand by electrolyzing water. This approach makes water a primary logistics commodity that must be managed carefully. Chemical reduction of metabolic carbon dioxide (CO2) provides a method of recycling oxygen thereby reducing the net ARS water demand and therefore minimizing logistics needs. Multiple methods have been proposed to achieve this recovery and have been reported in the literature. However, depending on the architecture and the technology approach, "oxygen recovery" can be defined in various ways. This discontinuity makes it difficult to compare technologies directly. In an effort to clarify community discussions of Oxygen Recovery, we propose specific definitions and describe the methodology used to arrive at those definitions. Additionally, we discuss key performance parameters for Oxygen Recovery technology development including challenges with comparisons to state-of-the-art.

Abrupt termination of Marine Isotope Stage 16 (Termination VII) at 631.5 ka in Santa Barbara Basin, Californi

USGS Publications Warehouse

Dean, Walter E.; Kennett, James P.; Behl, Richard J.; Nicholson, Craig; Sorlien, Christopher C.

2015-01-01

The Marine Isotope Stage 16–15 boundary (Termination VII) is the first deglacial warming step of the late Quaternary following the mid-Pleistocene transition (MPT), when 41 kyr climatic cycles shifted to strong 100 kyr cycles. The detailed structure of this important climatic event has remained unknown until now. Core MV0508-19JPC from Santa Barbara Basin, California, contains a decadal-scale climatic and geochemical sediment record of 4000 years duration that includes the early part of this deglacial episode. This record reveals that the climatic shift during the early deglacial occurred rapidly (<700 years), in a progression of three abrupt warming steps. The onset of Marine Isotope Stage (MIS) 15 was remarkably abrupt with 4–5°C sea surface warming in ~50 years. The deglacial sequence contains the well-dated Lava Creek tephra (631.3 ± 4 ka) from Yellowstone Caldera used to date the onset of Termination VII at 631.5 ka. The late MIS 16 and early MIS 15 interval exhibits multiple decadal-scale negative excursions in δ13C of planktic foraminifera, likely the result of repeated discharges of methane from methane hydrates associated with both ocean warming and low sea level. A warm interstadial that interrupts late MIS 16 is marked by elevated concentrations of redox-sensitive elements indicating sulfidic, oxygen-deficient bottom and pore-waters, and elevated concentrations of total organic carbon and Cd, reflecting increased surface productivity. Unlike younger sediments on the California margin, these indicators of increased productivity and low dissolved oxygen do not consistently correspond with each other or with preserved laminations, possibly reflecting instability of a still evolving ocean-atmosphere system following the MPT.

Chrysanthemum flower-like NiCo2O4-nitrogen doped graphene oxide composite: an efficient electrocatalyst for lithium-oxygen and zinc-air batteries.

PubMed

Moni, Prabu; Hyun, Suyeon; Vignesh, Ahilan; Shanmugam, Sangaraju

2017-07-06

Chrysanthemum flower-like NiCo 2 O 4 -nitrogen doped graphene oxide composite material has been explored as a bifunctional cathode electrocatalyst for aqueous zinc-air and non-aqueous lithium-oxygen batteries. This cathode exhibits maximum discharge capacities of 712 and 15 046 mA h g -1 for zinc-air and lithium-oxygen batteries, respectively, with stable cycling over 50 cycles.

Biodegradation – Monitored Natural Attenuation (MNA) for Oxygenates: How it Evolved, why it Occurs and Using Stable Carbon Isotopes to Predict Plume Behavior

EPA Science Inventory

The organisms that degrade MtBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

MNA for Chlorinated Solvents and Fuel Oxygenates: Why It Occurs, How It Evolved, and Using Stable Carbon Isotopes to Predict Plume Behavior

EPA Science Inventory

The organisms that degrade MtBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

Women's fertility across the cycle increases the short-term attractiveness of creative intelligence.

PubMed

Haselton, Martie G; Miller, Geoffrey F

2006-03-01

Male provisioning ability may have evolved as a "good dad" indicator through sexual selection, whereas male creativity may have evolved partly as a "good genes" indicator. If so, women near peak fertility (midcycle) should prefer creativity over wealth, especially in short-term mating. Forty-one normally cycling women read vignettes describing creative but poor men vs. uncreative but rich men. Women's estimated fertility predicted their short-term (but not long-term) preference for creativity over wealth, in both their desirability ratings of individual men (r=.40, p<.01) and their forced-choice decisions between men (r=.46, p<.01). These preliminary results are consistent with the view that creativity evolved at least partly as a good genes indicator through mate choice.

Sex as a response to oxidative stress: a twofold increase in cellular reactive oxygen species activates sex genes.

PubMed

Nedelcu, Aurora M; Marcu, Oana; Michod, Richard E

2004-08-07

Organisms are constantly subjected to factors that can alter the cellular redox balance and result in the formation of a series of highly reactive molecules known as reactive oxygen species (ROS). As ROS can be damaging to biological structures, cells evolved a series of mechanisms (e.g. cell-cycle arrest, programmed cell death) to respond to high levels of ROS (i.e. oxidative stress). Recently, we presented evidence that in a facultatively sexual lineage--the multicellular green alga Volvox carteri--sex is an additional response to increased levels of stress, and probably ROS and DNA damage. Here we show that, in V. carteri, (i) sex is triggered by an approximately twofold increase in the level of cellular ROS (induced either by the natural sex-inducing stress, namely heat, or by blocking the mitochondrial electron transport chain with antimycin A), and (ii) ROS are responsible for the activation of sex genes. As most types of stress result in the overproduction of ROS, we believe that our findings will prove to extend to other facultatively sexual lineages, which could be indicative of the ancestral role of sex as an adaptive response to stress and ROS-induced DNA damage. Copyright 2004 The Royal Society

Examination of oxygen release from plants in constructed wetlands in different stages of wetland plant life cycle.

PubMed

Zhang, Jian; Wu, Haiming; Hu, Zhen; Liang, Shuang; Fan, Jinlin

2014-01-01

The quantification of oxygen release by plants in different stages of wetland plant life cycle was made in this study. Results obtained from 1 year measurement in subsurface wetland microcosms demonstrated that oxygen release from Phragmites australis varied from 108.89 to 404.44 mg O₂/m(2)/d during the different periods from budding to dormancy. Plant species, substrate types, and culture solutions had a significant effect on the capacity of oxygen release of wetland plants. Oxygen supply by wetland plants was estimated to potentially support a removal of 300.37 mg COD/m(2)/d or 55.87 mg NH₄-N/m(2)/d. According to oxygen balance analysis, oxygen release by plants could provide 0.43-1.12% of biochemical oxygen demand in typical subsurface-flow constructed wetlands (CWs). This demonstrates that oxygen release of plants may be a potential source for pollutants removal especially in low-loaded CWs. The results make it possible to quantify the role of plants in wastewater purification.

Metatranscriptomic analysis of a high-sulfide aquatic spring reveals insights into sulfur cycling and unexpected aerobic metabolism

PubMed Central

Elshahed, Mostafa S.; Najar, Fares Z.; Krumholz, Lee R.

2015-01-01

Zodletone spring is a sulfide-rich spring in southwestern Oklahoma characterized by shallow, microoxic, light-exposed spring water overlaying anoxic sediments. Previously, culture-independent 16S rRNA gene based diversity surveys have revealed that Zodletone spring source sediments harbor a highly diverse microbial community, with multiple lineages putatively involved in various sulfur-cycling processes. Here, we conducted a metatranscriptomic survey of microbial populations in Zodletone spring source sediments to characterize the relative prevalence and importance of putative phototrophic, chemolithotrophic, and heterotrophic microorganisms in the sulfur cycle, the identity of lineages actively involved in various sulfur cycling processes, and the interaction between sulfur cycling and other geochemical processes at the spring source. Sediment samples at the spring’s source were taken at three different times within a 24-h period for geochemical analyses and RNA sequencing. In depth mining of datasets for sulfur cycling transcripts revealed major sulfur cycling pathways and taxa involved, including an unexpected potential role of Actinobacteria in sulfide oxidation and thiosulfate transformation. Surprisingly, transcripts coding for the cyanobacterial Photosystem II D1 protein, methane monooxygenase, and terminal cytochrome oxidases were encountered, indicating that genes for oxygen production and aerobic modes of metabolism are actively being transcribed, despite below-detectable levels (<1 µM) of oxygen in source sediment. Results highlight transcripts involved in sulfur, methane, and oxygen cycles, propose that oxygenic photosynthesis could support aerobic methane and sulfide oxidation in anoxic sediments exposed to sunlight, and provide a viewpoint of microbial metabolic lifestyles under conditions similar to those seen during late Archaean and Proterozoic eons. PMID:26417542

Metatranscriptomic analysis of a high-sulfide aquatic spring reveals insights into sulfur cycling and unexpected aerobic metabolism.

PubMed

Spain, Anne M; Elshahed, Mostafa S; Najar, Fares Z; Krumholz, Lee R

2015-01-01

Zodletone spring is a sulfide-rich spring in southwestern Oklahoma characterized by shallow, microoxic, light-exposed spring water overlaying anoxic sediments. Previously, culture-independent 16S rRNA gene based diversity surveys have revealed that Zodletone spring source sediments harbor a highly diverse microbial community, with multiple lineages putatively involved in various sulfur-cycling processes. Here, we conducted a metatranscriptomic survey of microbial populations in Zodletone spring source sediments to characterize the relative prevalence and importance of putative phototrophic, chemolithotrophic, and heterotrophic microorganisms in the sulfur cycle, the identity of lineages actively involved in various sulfur cycling processes, and the interaction between sulfur cycling and other geochemical processes at the spring source. Sediment samples at the spring's source were taken at three different times within a 24-h period for geochemical analyses and RNA sequencing. In depth mining of datasets for sulfur cycling transcripts revealed major sulfur cycling pathways and taxa involved, including an unexpected potential role of Actinobacteria in sulfide oxidation and thiosulfate transformation. Surprisingly, transcripts coding for the cyanobacterial Photosystem II D1 protein, methane monooxygenase, and terminal cytochrome oxidases were encountered, indicating that genes for oxygen production and aerobic modes of metabolism are actively being transcribed, despite below-detectable levels (<1 µM) of oxygen in source sediment. Results highlight transcripts involved in sulfur, methane, and oxygen cycles, propose that oxygenic photosynthesis could support aerobic methane and sulfide oxidation in anoxic sediments exposed to sunlight, and provide a viewpoint of microbial metabolic lifestyles under conditions similar to those seen during late Archaean and Proterozoic eons.

An increase in prefrontal oxygenation at the start of voluntary cycling exercise was observed independently of exercise effort and muscle mass.

PubMed

Asahara, Ryota; Endo, Kana; Liang, Nan; Matsukawa, Kanji

2018-05-31

We have reported using near-infrared spectroscopy that an increase in prefrontal oxygenated-hemoglobin concentration (Oxy-Hb) at the start of cycling exercise has relation to central command, defined as a feedforward signal descending from higher brain centers. The final output of central command evokes the exercise effort-dependent cardiovascular responses. If the prefrontal cortex may output the final signal of central command toward the autonomic nervous system, the prefrontal oxygenation should increase depending on exercise effort. To test the hypothesis, we investigated the effects of exercise intensity and muscle mass on prefrontal oxygenation in 13 subjects. The subjects performed one- or two-legged cycling at various relative intensities for 1 min. The prefrontal Oxy-Hb and cardiovascular variables were simultaneously measured during exercise. The increase in cardiac output and the decrease in total peripheral resistance at the start of one- and two-legged cycling were augmented in proportion to exercise intensity and muscle mass recruitment. The prefrontal Oxy-Hb increased at the start of voluntary cycling, while such increase was not developed during passive cycling. Mental imagery of cycling also increased the prefrontal Oxy-Hb, concomitantly with peripheral muscle vasodilatation. However, the increase in prefrontal Oxy-Hb at the start of voluntary cycling seemed independent of exercise intensity and muscle mass recruitment. It is likely that the increased prefrontal activity at the start of cycling exercise is not representative of the final output signal of central command itself toward the autonomic nervous system but may trigger neuronal activity in the caudal brain responsible for the generation of central command.

The evolving magnetic topology of τ Boötis

NASA Astrophysics Data System (ADS)

Mengel, M. W.; Fares, R.; Marsden, S. C.; Carter, B. D.; Jeffers, S. V.; Petit, P.; Donati, J.-F.; Folsom, C. P.; BCool Collaboration

2016-07-01

We present six epochs of spectropolarimetric observations of the hot-Jupiter-hosting star τ Boötis that extend the exceptional previous multiyear data set of its large-scale magnetic field. Our results confirm that the large-scale magnetic field of τ Boötis varies cyclicly, with the observation of two further magnetic reversals; between 2013 December and 2014 May and between 2015 January and March. We also show that the field evolves in a broadly solar-type manner in contrast to other F-type stars. We further present new results which indicate that the chromospheric activity cycle and the magnetic activity cycles are related, which would indicate a very rapid magnetic cycle. As an exemplar of long-term magnetic field evolution, τ Boötis and this long-term monitoring campaign presents a unique opportunity for studying stellar magnetic cycles.

Use of Isolated Mitochondria and Pulmonary Artery Endothelial Cell Systems in Studies of Oxygen Utilization and the Effects of Hemoglobin-Based Oxygen Carriers

DTIC Science & Technology

2008-07-16

mitochondria through the monocarboxylate transporter and feed in to the Kreb’s cycle to yield 34 ATPs via oxidative phosphorylation as follows (assuming a... Krebs (tricarboxylic acid) cycle enzyme, and is found mainly in the mitochondrial matrix (8). Therefore, its measured enzymatic activity serves as an...APPROVAL SHEET Title of Thesis: "Use of Isolated Mitochondria and Pulmonary Artery Endothelial Cell Systems in Studies of Oxygen Utilization and the

Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte.

PubMed

Luo, Jia-Yan; Cui, Wang-Jun; He, Ping; Xia, Yong-Yao

2010-09-01

Aqueous lithium-ion batteries may solve the safety problem associated with lithium-ion batteries that use highly toxic and flammable organic solvents, and the poor cycling life associated with commercialized aqueous rechargeable batteries such as lead-acid and nickel-metal hydride systems. But all reported aqueous lithium-ion battery systems have shown poor stability: the capacity retention is typically less than 50% after 100 cycles. Here, the stability of electrode materials in an aqueous electrolyte was extensively analysed. The negative electrodes of aqueous lithium-ion batteries in a discharged state can react with water and oxygen, resulting in capacity fading upon cycling. By eliminating oxygen, adjusting the pH values of the electrolyte and using carbon-coated electrode materials, LiTi(2)(PO(4))(3)/Li(2)SO(4)/LiFePO(4) aqueous lithium-ion batteries exhibited excellent stability with capacity retention over 90% after 1,000 cycles when being fully charged/discharged in 10 minutes and 85% after 50 cycles even at a very low current rate of 8 hours for a full charge/discharge offering an energy storage system with high safety, low cost, long cycling life and appropriate energy density.

Oxidative elemental cycling under the low O2 Eoarchean atmosphere

PubMed Central

Frei, Robert; Crowe, Sean A.; Bau, Michael; Polat, Ali; Fowle, David A.; Døssing, Lasse N.

2016-01-01

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3–2.9 Gyr ago. 3.8–3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8–3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology. PMID:26864443

Lunar production of oxygen by electrolysis

NASA Technical Reports Server (NTRS)

Keller, Rudolf

1991-01-01

Two approaches to prepare oxygen from lunar resources by direct electrolysis are discussed. Silicates can be melted or dissolved in a fused salt and electrolyzed with oxygen evolved at the anode. Direct melting and electrolysis is potentially a very simple process, but high temperatures of 1400-1500 C are required, which aggravates materials problems. Operating temperatures can be lowered to about 1000 C by employing a molten salt flux. In this case, however, losses of electrolyte components must be avoided. Experimentation on both approaches is progressing.

Orbital-Dependent Density Functionals for Chemical Catalysis

DTIC Science & Technology

2014-10-17

noncollinear density functional theory to show that the low-spin state of Mn3 in a model of the oxygen -evolving complex of photosystem II avoids...DK, which denotes the cc-pV5Z-DK basis set for 3d metals and hydrogen and the ma-cc- pV5Z-DK basis set for oxygen ) and to nonrelativistic all...cc-pV5Z basis set for oxygen ). As compared to NCBS-DK results, all ECP calculations perform worse than def2-TZVP all-electron relativistic

Hydrogen-Oxygen PEM Regenerative Fuel Cell at NASA Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.

2004-01-01

The NASA Glenn Research Center has constructed a closed-cycle hydrogen-oxygen PEM regenerative fuel cell (RFC) to explore its potential use as an energy storage device for a high altitude solar electric aircraft. Built up over the last 2 years from specialized hardware and off the shelf components the Glenn RFC is a complete "brassboard" energy storage system which includes all the equipment required to (1) absorb electrical power from an outside source and store it as pressurized hydrogen and oxygen and (2) make electrical power from the stored gases, saving the product water for re-use during the next cycle. It consists of a dedicated hydrogen-oxygen fuel cell stack and an electrolyzer stack, the interconnecting plumbing and valves, cooling pumps, water transfer pumps, gas recirculation pumps, phase separators, storage tanks for oxygen (O2) and hydrogen (H2), heat exchangers, isolation valves, pressure regulators, nitrogen purge provisions, instrumentation, and other components. It specific developmental functions include: (1) Test fuel cells and fuel cell components under repeated closed-cycle operation (nothing escapes; everything is used over and over again). (2) Simulate diurnal charge-discharge cycles (3) Observe long-term system performance and identify degradation and loss mechanisms. (4) Develop safe and convenient operation and control strategies leading to the successful development of mission-capable, flight-weight RFC's.

Pluronic F127 as auxiliary template for preparing nitrogen and oxygen dual doped mesoporous carbon cathode of lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Wu, Junwei; Liu, Yanchen; Cui, Yanhui; Ouyang, Jue; Baker, Andrew P.; Li, Zuohua; Zhang, Huayu

2018-02-01

Two mesoporous carbon foam (MCF) with nitrogen and oxygen dual doped are fabricated through facile templated hydrothermal process. One using fumed silica as single template is named S-MCF, and another using fumed silica and Pluronic F127 as double templates is named D-MCF. When using Pluronic F127 as an auxiliary template, the D-MCF shows different porous architecture and surface chemical nature from S-MCF, thus they behave differently as cathode materials in Li-O2 batteries. The D-MCF electrode exhibits a slight lower discharge capacity and an increased overpotential than that of S-SCF due to the decreased surface area and oxygen content. However, a better cycle stability was proved for the D-MCF electrode because of its higher nitrogen and lower oxygen content. When further composited with RuO2 nanoparticles, the RuO2/D-MCF cathode can operate 160 cycles with capacity cutoff of 500 mAh g-1, and this prolonged cycle life, compared to the 102 cycles of S-MCF cathode, verifies the superior electrochemical stability of D-MCF further and illuminates the crucial role of carbon substrate in the cathodes of Li-O2 batteries.

The effect of light:dark cycles of medium frequency on photosynthesis by Chlorella vulgaris and the implications for waste stabilisation pond design and performance.

PubMed

Ratchford, I A J; Fallowfield, H J

2003-01-01

The effect of light/dark (L:D) cycle times on the recovery from photoinhibition of green micro-alga Chlorella vulgaris (CCAP211/11c) and the cyanobacterium Synechococcus (CCAP1479/5) was investigated using an irradiated, temperature controlled oxygen electrode. The onset of photoinhibition in both organisms occurred at irradiances > 300 micromol m(-2)s(-1) at temperatures >15 degrees C. Light/dark cycle times were controlled independently using a relay timer and shutter placed between the quartz iodide light source and the oxygen electrode chamber. Oxygen evolution decreased rapidly when cells were continuously irradiated at 300, 500 and 750 micromol m(-2)s(-1). However, Chlorella cells irradiated at 300, 500 and 750 micromol m(-2)s(-1)on a L:D cycle of 60s:20s, 30s:60s and 60s: 120s respectively, maintained a constant rate of oxygen evolution over a 24 h incubation period. Exposure time to a given incident irradiance rather than the total light dose received appeared to determine the effect of light/dark cycle times on photosynthesis. A relationship was established between L:D ratio required to maintain constant oxygen production and incident photon flux density. The results suggest that the adverse effects of high irradiances on algae near the surface of a stratified waste stabilisation pond might be ameliorated by controlled mixing of algal cells through the depth of the pond.

Nonadiabatic one-electron transfer mechanism for the O-O bond formation in the oxygen-evolving complex of photosystem II

NASA Astrophysics Data System (ADS)

Shoji, Mitsuo; Isobe, Hiroshi; Shigeta, Yasuteru; Nakajima, Takahito; Yamaguchi, Kizashi

2018-04-01

The reaction mechanism of the O2 formation in the S4 state of the oxygen-evolving complex of photosystem II was clarified at the quantum mechanics/molecular mechanics (QM/MM) level. After the Yz (Y161) oxidation and the following proton transfer in the S3 state, five reaction steps are required to produce the molecular dioxygen. The highest barrier step is the first proton transfer reaction (0 → 1). The following reactions involving electron transfers were precisely analyzed in terms of their energies, structures and spin densities. We found that the one-electron transfer from the Mn4Ca cluster to Y161 triggers the O-O sigma bond formation.

Effects of combined high intensity arm and leg training on performance and cardio-respiratory measures.

PubMed

Zinner, Christoph; Sperlich, Billy; Born, Dennis-Peter; Michels, Guido

2017-01-01

The purpose of this study was to investigate the effects of combined arm and leg high-intensity low-volume interval training (HIITarm+leg) on maximal oxygen uptake, myocardial measures (i.e. stroke volume, cardiac output, ejection fraction), Tissue Oxygenation Index (TOI) of the vastus lateralis and triceps brachii, as well as power output in comparison to leg HIIT (HIITleg) only. The 20 healthy, male and female volunteers completed six sessions of either HIITleg on a cycle ergometer or HIITarm+leg on an arm and leg cycle ergometer. During pre- and post-testing, the volunteers completed a submaximal and incremental test to exhaustion on a cycle ergometer. Magnitude based interference revealed likely to very likely beneficial effects for HIITarm+leg compared to HIITleg in maximal oxygen uptake, cardiac measures as well peak power output. The TOI following HIITarm+leg demonstrated likely to very likely increased oxygenation in the triceps brachii or the vastus lateralis when compared to HIITleg. The results suggest that six sessions of HIITarm+leg may likely to very likely improve maximal oxygen uptake, some inotropy-related cardiac measures with improved tissue oxygenation of the triceps brachii and vastus lateralis muscles resulting in greater leg peak power output.

Singlet oxygen generator for a supersonic chemical oxygen iodine laser: parametric study and recovery of chemicals

NASA Astrophysics Data System (ADS)

Spalek, Otomar; Kodymova, Jarmila

1997-04-01

A jet singlet oxygen generator for a supersonic chemical oxygen-iodine laser was studied including singlet delta oxygen, O2(1(Delta) g), and residual chlorine concentration measurements. The investigation was intended mainly for a water vapor measurement in gas effluent of generator in dependence on properties of liquid jets: a chemical composition and temperature of the input liquid (alkaline solution of hydrogen peroxide), a liquid jets diameter and their geometrical arrangement. Effects of these parameters on output power of a small-scale supersonic laser were studied as well. Possible approaches to a chemical fuels management in a chemical oxygen-iodine laser for industrial applications are considered. An 'open loop' cycle with a possible use of sodium hydroxide, and a 'closed loop' cycle with a regeneration of both potassium hydroxide and hydrogen peroxide are discussed.

Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle

NASA Astrophysics Data System (ADS)

Casciotti, Karen L.

2016-01-01

The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status.

Mode of exercise and sex are not important for oxygen consumption during and in recovery from sprint interval training.

PubMed

Townsend, Logan K; Couture, Katie M; Hazell, Tom J

2014-12-01

Most sprint interval training (SIT) research involves cycling as the mode of exercise and whether running SIT elicits a similar excess postexercise oxygen consumption (EPOC) response to cycling SIT is unknown. As running is a more whole-body-natured exercise, the potential EPOC response could be greater when using a running session compared with a cycling session. The purpose of the current study was to determine the acute effects of a running versus cycling SIT session on EPOC and whether potential sex differences exist. Sixteen healthy recreationally active individuals (8 males and 8 females) had their gas exchange measured over ∼2.5 h under 3 experimental sessions: (i) a cycle SIT session, (ii) a run SIT session, and (iii) a control (CTRL; no exercise) session. Diet was controlled. During exercise, both SIT modes increased oxygen consumption (cycle: male, 1.967 ± 0.343; female, 1.739 ± 0.296 L·min(-1); run: male, 2.169 ± 0.369; female, 1.791 ± 0.481 L·min(-1)) versus CTRL (male, 0.425 ± 0.065 L·min(-1); female, 0.357 ± 0.067; P < 0.001), but not compared with each other (P = 0.234). In the first hour postexercise, oxygen consumption was still increased following both run (male, 0.590 ± 0.065; female, 0.449 ± 0.084) and cycle SIT (male, 0.556 ± 0.069; female, 0.481 ± 0.110 L·min(-1)) versus CTRL and oxygen consumption was maintained through the second hour postexercise (CTRL: male, 0.410 ± 0.048; female, 0.332 ± 0.062; cycle: male, 0.430 ± 0.047; female, 0.395 ± 0.087; run: male, 0.463 ± 0.051; female, 0.374 ± 0.087 L·min(-1)). The total EPOC was not significantly different between modes of exercise or males and females (P > 0.05). Our data demonstrate that the mode of exercise during SIT (cycling or running) is not important to O2 consumption and that males and females respond similarly.

The physiological and biomechanical differences between double poling and G3 skating in world class cross-country skiers.

PubMed

Sandbakk, Øyvind; Leirdal, Stig; Ettema, Gertjan

2015-03-01

The current study compared differences in cycle characteristics, energy expenditure and peak speed between double poling (DP) and G3 skating. Eight world class male sprint skiers performed a 5-min submaximal test at 16 km h(-1) and an incremental test to exhaustion at a 5% incline during treadmill roller skiing with two different techniques: DP where all propulsion comes from poling, and G3 skating where leg skating is added to each double poling movement. Video analyses determined cycle characteristics; respiratory parameters and blood lactate concentration determined the physiological responses. G3 skating resulted in 16% longer cycle lengths at 16% lower cycle rates, whereas oxygen uptake was independent of technique during submaximal roller skiing. The corresponding advantages for G3 skating during maximal roller skiing were reflected in 14% higher speed, 30% longer cycle length at 16% lower cycle rate and 11% higher peak oxygen uptake (all p < 0.05). Compared to DP approximately 14% higher speed was achieved when leg push-offs were added in G3 skating. This was done by major increases in cycle lengths at slightly lower cycle rates and a higher aerobic energy delivery. However, the oxygen uptake for a given submaximal speed was not affected by technique although higher cycle rate was used in DP.

Thermally regenerative hydrogen/oxygen fuel cell power cycles

NASA Technical Reports Server (NTRS)

Morehouse, J. H.

1986-01-01

Two innovative thermodynamic power cycles are analytically examined for future engineering feasibility. The power cycles use a hydrogen-oxygen fuel cell for electrical energy production and use the thermal dissociation of water for regeneration of the hydrogen and oxygen. The TDS (thermal dissociation system) uses a thermal energy input at over 2000 K to thermally dissociate the water. The other cycle, the HTE (high temperature electrolyzer) system, dissociates the water using an electrolyzer operating at high temperature (1300 K) which receives its electrical energy from the fuel cell. The primary advantages of these cycles is that they are basically a no moving parts system, thus having the potential for long life and high reliability, and they have the potential for high thermal efficiency. Both cycles are shown to be classical heat engines with ideal efficiency close to Carnot cycle efficiency. The feasibility of constructing actual cycles is investigated by examining process irreversibilities and device efficiencies for the two types of cycles. The results show that while the processes and devices of the 2000 K TDS exceed current technology limits, the high temperature electrolyzer system appears to be a state-of-the-art technology development. The requirements for very high electrolyzer and fuel cell efficiencies are seen as determining the feasbility of the HTE system, and these high efficiency devices are currently being developed. It is concluded that a proof-of-concept HTE system experiment can and should be conducted.

The oxygen minimum zone of the eastern South Pacific

NASA Astrophysics Data System (ADS)

Ulloa, Osvaldo; Pantoja, Silvio

2009-07-01

In spite of the fact that oxygen-deficient waters with ⩽20 μM of dissolved oxygen—known as oxygen minimum zones (OMZs)—occupy only ˜1% of the volume of the global ocean, they disproportionately affect global biogeochemical cycles, particularly the nitrogen cycle. The macrobiota diversity in OMZs is low, but the fauna that do inhabit these regions present special adaptations to the low-oxygen conditions. Conversely, microbial communities in the OMZ water column and sediments are abundant and phylogenetically and metabolically very diverse, and microbial processes occurring therein (e.g., denitrification, anammox, and organic matter degradation) are important for global marine biogeochemical cycles. In this introductory article, we present the collection of papers for the special volume on the OMZ of the eastern South Pacific, one of the three main open-ocean oxygen-deficient regions of the global ocean. These papers deal with aspects of regional oceanography, inorganic and organic geochemistry, ecology, and the biochemistry of micro and macro organisms—both in the plankton and in the sediments—and past changes in the fish scales preserved in the sediments bathed by OMZ waters.

Did meiosis evolve before sex and the evolution of eukaryotic life cycles?

PubMed

Niklas, Karl J; Cobb, Edward D; Kutschera, Ulrich

2014-11-01

Biologists have long theorized about the evolution of life cycles, meiosis, and sexual reproduction. We revisit these topics and propose that the fundamental difference between life cycles is where and when multicellularity is expressed. We develop a scenario to explain the evolutionary transition from the life cycle of a unicellular organism to one in which multicellularity is expressed in either the haploid or diploid phase, or both. We propose further that meiosis might have evolved as a mechanism to correct for spontaneous whole-genome duplication (auto-polyploidy) and thus before the evolution of sexual reproduction sensu stricto (i.e. the formation of a diploid zygote via the fusion of haploid gametes) in the major eukaryotic clades. In addition, we propose, as others have, that sexual reproduction, which predominates in all eukaryotic clades, has many different advantages among which is that it produces variability among offspring and thus reduces sibling competition. © 2014 WILEY Periodicals, Inc.

Bicarbonate may Be required for ligation of manganese in the oxygen-evolving complex of photosystem II.

PubMed

Klimov, V V; Hulsebosch, R J; Allakhverdiev, S I; Wincencjusz, H; van Gorkom, H J; Hoff, A J

1997-12-23

It was previously shown in the photosystem II membrane preparation DT-20 that photoxidation of the oxygen-evolving manganese cluster was blocked by 0.1 mM formate, unless 0.2 mM bicarbonate was present as well [Wincencjusz, H., Allakhverdiev, S. I., Klimov, V. V., and Van Gorkom, H. J. (1996) Biochim. Biophys. Acta 1273, 1-3]. Here it is shown by measurements of EPR signal II that oxidation of the secondary electron donor, YZ, is not inhibited. However, the reduction of is greatly slowed and occurs largely by back reaction with reduced acceptors. Bicarbonate is shown to prevent the loss of fast electron donation to . The release of about one or two free Mn2+ per photosystem II during formate treatment, and the fact that these effects are mimicked by Mn-depletion, suggests that formate may act by replacing a bicarbonate which is essential for Mn binding. Irreversible light-induced rebinding in an EPR-silent form of Mn2+ that was added to Mn-depleted DT-20 was indeed found to depend on the presence of bicarbonate, as did the reconstitution in such material of both the fast electron donation to and the UV absorbance changes characteristic of a functional oxygen-evolving complex. It is concluded that bicarbonate may be an essential ligand of the functional Mn cluster.

Heat-induced reorganization of the structure of photosystem II membranes: role of oxygen evolving complex.

PubMed

Busheva, Mira; Tzonova, Iren; Stoitchkova, Katerina; Andreeva, Atanaska

2012-12-05

The sensitivity of the green plants' photosystem II (PSII) to high temperatures is investigated in PSII enriched membranes and in membranes, from which the oxygen evolving complex is removed. Using steady-state 77 K fluorescence and resonance Raman spectroscopy we analyze the interdependency between the temperature-driven changes in structure and energy distribution in the PSII supercomplex. The results show that the heat treatment induces different reduction of the 77 K fluorescence emission in both types of investigated membranes: (i) an additional considerable decrease of the overall fluorescence emission in Tris-washed membranes as compared to the native membranes; (ii) a transition point at 42°C(,) observed only in native membranes; (iii) a sharp reduction of the PSII core fluorescence in Tris-washed membranes at temperatures higher than 50°C; (iv) a 3 nm red-shift of F700 band's maximum in Tris-washed membranes already at 20°C and its further shift by 1 nm at temperature increase. Both treatments intensified their action by increasing the aggregation and dissociation of the peripheral light harvesting complexes. The oxygen-evolving complex, in addition to its main function to produce O(2), increases the thermal stability of PSII core by strengthening the connection between the core and the peripheral antenna proteins and by keeping their structural integrity. Copyright © 2012 Elsevier B.V. All rights reserved.

Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses.

PubMed

Suga, Michihiro; Akita, Fusamichi; Hirata, Kunio; Ueno, Go; Murakami, Hironori; Nakajima, Yoshiki; Shimizu, Tetsuya; Yamashita, Keitaro; Yamamoto, Masaki; Ago, Hideo; Shen, Jian-Ren

2015-01-01

Photosynthesis converts light energy into biologically useful chemical energy vital to life on Earth. The initial reaction of photosynthesis takes place in photosystem II (PSII), a 700-kilodalton homodimeric membrane protein complex that catalyses photo-oxidation of water into dioxygen through an S-state cycle of the oxygen evolving complex (OEC). The structure of PSII has been solved by X-ray diffraction (XRD) at 1.9 ångström resolution, which revealed that the OEC is a Mn4CaO5-cluster coordinated by a well defined protein environment. However, extended X-ray absorption fine structure (EXAFS) studies showed that the manganese cations in the OEC are easily reduced by X-ray irradiation, and slight differences were found in the Mn-Mn distances determined by XRD, EXAFS and theoretical studies. Here we report a 'radiation-damage-free' structure of PSII from Thermosynechococcus vulcanus in the S1 state at a resolution of 1.95 ångströms using femtosecond X-ray pulses of the SPring-8 ångström compact free-electron laser (SACLA) and hundreds of large, highly isomorphous PSII crystals. Compared with the structure from XRD, the OEC in the X-ray free electron laser structure has Mn-Mn distances that are shorter by 0.1-0.2 ångströms. The valences of each manganese atom were tentatively assigned as Mn1D(III), Mn2C(IV), Mn3B(IV) and Mn4A(III), based on the average Mn-ligand distances and analysis of the Jahn-Teller axis on Mn(III). One of the oxo-bridged oxygens, O5, has significantly longer distances to Mn than do the other oxo-oxygen atoms, suggesting that O5 is a hydroxide ion instead of a normal oxygen dianion and therefore may serve as one of the substrate oxygen atoms. These findings provide a structural basis for the mechanism of oxygen evolution, and we expect that this structure will provide a blueprint for the design of artificial catalysts for water oxidation.

Theoretical reflections on the structural polymorphism of the oxygen-evolving complex in the S2 state and the correlations to substrate water exchange and water oxidation mechanism in photosynthesis.

PubMed

Guo, Yu; Li, Hui; He, Lan-Lan; Zhao, Dong-Xia; Gong, Li-Dong; Yang, Zhong-Zhi

2017-10-01

The structural polymorphism of the oxygen-evolving complex is of great significance to photosynthetic water oxidation. Employing density functional theory calculations, we have made further advisement on the interconversion mechanism of O5 transfer in the S 2 state, mainly focusing on the potentiality of multi-state reactivity and spin transitions. Then, O5 protonation is proven impossible in S 2 for irreversibility of the interconversion, which serves as an auxiliary judgment for the protonation state of O5 in S 1 . Besides, the structural polymorphism could also be archived by alternative mechanisms involving Mn3 ligand exchange, one of which with Mn3(III) makes sense to substrate water exchange in S 2 , although being irresponsible for the derivations of the observed EPR signals. During the water exchange, high-spin states would prevail to facilitate electron transfer between the ferromagnetically coupled Mn centers. In addition, water exchange in S 1 could account for the closed-cubane structure as the initial form entering S 2 at cryogenic temperatures. With regard to water oxidation, the structural flexibility and variability in both S 2 and S 3 guarantee smooth W2-O5 coupling in S 4 , according to the substrate assignments from water exchange kinetics. Within this theoretical framework, the new XFEL findings on S 1 -S 3 can be readily rationalized. Finally, an alternative mechanistic scenario for OO bond formation with ·OH radical near O4 is presented, followed by water binding to the pivot Mn4(III) from O4 side during S 4 -S 0 . This may diversify the substrate sources combined with the Ca channel in water delivery for the forthcoming S-cycle. Copyright © 2017. Published by Elsevier B.V.

Oxygen Minimum Zones in Miniature: Microbial Community Diversity, Activity, and Assembly Across Oxygen Gradients in Meromictic Marine Lakes, Palau

NASA Astrophysics Data System (ADS)

Beman, J. M.

2016-02-01

Oxygen minimum zones (OMZs) play a central role in biogeochemical cycles and are expanding as a consequence of climate change, yet our understanding of these changes is limited by a lack of systematic analyses of low-oxygen ecosystems. In particular, forecasting biogeochemical feedbacks to deoxygenation requires detailed knowledge of microbial community assembly and activity as oxygen declines. Marine `lakes'—isolated bodies of seawater surrounded by land—are an ideal comparative system, as they provide a pronounced oxygen gradient extending from well-mixed, holomictic lakes to stratified, meromictic lakes that vary in their extent of anoxia. We examined 13 marine lakes using pyrosequencing of 16S rRNA genes, quantitative PCR for nitrogen (N)- and sulfur (S)-cycling functional genes and groups, and N- and carbon (C)-cycling rate measurements. All lakes were inhabited by well-known marine bacteria, demonstrating the broad relevance of this study system. Microbial diversity was typically highest in the anoxic monimolimnion of meromictic lakes, with marine cyanobacteria, SAR11, and other common bacteria replaced by anoxygenic phototrophs, sulfate-reducing bacteria (SRBs), and SAR406 in the monimolimnion. Denitrifier nitrite reductase (nirS) genes were also detected alongside high abundances (>106 ml-1) of dissimilatory sulfite reductase (dsrA) genes from SRBs in the monimolimnion. Sharp changes in community structure were linked to environmental gradients (constrained variation in redundancy analysis=76%) and deterministic processes dominated community assembly at all depths (nearest taxon index values >4). These results indicate that oxygen is a strong, deterministic driver of microbial community assembly. We also observed enhanced N- and C-cycling rates along the transition from hypoxic to anoxic to sulfidic conditions, suggesting that microbial communities form a positive feedback loop that may accelerate deoxygenation and OMZ expansion.

Understanding Side Reactions in K–O 2 Batteries for Improved Cycle Life

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Xiaodi; Lau, Kah Chun; Yu, Mingzhe

2014-10-20

Superoxide based metal-air (or metal-oxygen) batteries, including potassium and sodium-oxygen batteries, have emerged as promising alternative chemistries in the metal-air battery family because of much improved round-trip efficiencies (>90%). In order to improve the cycle life of these batteries, it is crucial to understand and control the side reactions between the electrodes and the electrolyte. For potassium-oxygen batteries using ether-based electrolytes, the side reactions on the potassium anode have been identified as the main cause of battery failure. The composition of the side products formed on the anode, including some reaction intermediates, have been identified and quantified. Combined experimental studiesmore » and density functional theory (DFT) calculations show the side reactions are likely driven by the interaction of potassium with ether molecules and the crossover of oxygen from the cathode. To inhibit these side reactions, the incorporation of a polymeric potassium ion selective membrane (Nafion-K+) as a battery separator is demonstrated that significantly improves the battery cycle life. The K-O-2 battery with the Nafion-K+ separator can be discharged and charged for more than 40 cycles without increases in charging overpotential.« less

Structural changes in the oxygen-evolving complex of photosystem II induced by the S 1 to S 2 transition: A combined XRD and QM/MM study

DOE PAGES

Askerka, Mikhail; Wang, Jimin; Brudvig, Gary W.; ...

2014-10-27

The S 1 → S 2 transition of the oxygen-evolving complex (OEC) of photosystem II does not involve the transfer of a proton to the lumen and occurs at cryogenic temperatures. Therefore, it is commonly thought to involve only Mn oxidation without any significant change in the structure of the OEC. Here, we analyze structural changes upon the S 1 → S 2 transition, as revealed by quantum mechanics/molecular mechanics methods and the isomorphous difference Fourier method applied to serial femtosecond X-ray diffraction data. Lastly, we find that the main structural change in the OEC is in the position ofmore » the dangling Mn and its coordination environment.« less

Veno-arterial extracorporeal membrane oxygenation for adult cardiovascular failure.

PubMed

Pellegrino, Vincent; Hockings, Lisen E; Davies, Andrew

2014-10-01

To examine the utility and technical challenges of applying veno-arterial extracorporeal membrane oxygenation for acute cardiovascular failure in adults with acute and chronic causes of heart failure. The role of mechanical circulatory support in acute cardiovascular continues to evolve as technology and clinical experience develop. There is increasing interest in the role of veno-arterial extracorporeal membrane oxygenation as a bridging therapy and as an adjunct to conventional cardiopulmonary resuscitation. Veno-arterial extracorporeal membrane oxygenation is an expensive, complex, resource intensive support. It is essential that its future use be guided by evidence obtained from centres that have demonstrated timely, safe support.

Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

DOEpatents

Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

DOEpatents

Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

PO2 cycling reduces diaphragm fatigue by attenuating ROS formation.

PubMed

Zuo, Li; Diaz, Philip T; Chien, Michael T; Roberts, William J; Kishek, Juliana; Best, Thomas M; Wagner, Peter D

2014-01-01

Prolonged muscle exposure to low PO2 conditions may cause oxidative stress resulting in severe muscular injuries. We hypothesize that PO2 cycling preconditioning, which involves brief cycles of diaphragmatic muscle exposure to a low oxygen level (40 Torr) followed by a high oxygen level (550 Torr), can reduce intracellular reactive oxygen species (ROS) as well as attenuate muscle fatigue in mouse diaphragm under low PO2. Accordingly, dihydrofluorescein (a fluorescent probe) was used to monitor muscular ROS production in real time with confocal microscopy during a lower PO2 condition. In the control group with no PO2 cycling, intracellular ROS formation did not appear during the first 15 min of the low PO2 period. However, after 20 min of low PO2, ROS levels increased significantly by ∼30% compared to baseline, and this increase continued until the end of the 30 min low PO2 condition. Conversely, muscles treated with PO2 cycling showed a complete absence of enhanced fluorescence emission throughout the entire low PO2 period. Furthermore, PO2 cycling-treated diaphragm exhibited increased fatigue resistance during prolonged low PO2 period compared to control. Thus, our data suggest that PO2 cycling mitigates diaphragm fatigue during prolonged low PO2. Although the exact mechanism for this protection remains to be elucidated, it is likely that through limiting excessive ROS levels, PO2 cycling initiates ROS-related antioxidant defenses.

Breaking wind to survive: fishes that breathe air with their gut.

PubMed

Nelson, J A

2014-03-01

Several taxonomically disparate groups of fishes have evolved the ability to extract oxygen from the air with elements of their gut. Despite perceived difficulties with balancing digestive and respiratory function, gut air breathing (GAB) has evolved multiple times in fishes and several GAB families are among the most successful fish families in terms of species numbers. When gut segments evolve into an air-breathing organ (ABO), there is generally a specialized region for exchange of gases where the gut wall has diminished, vascularization has increased, capillaries have penetrated into the luminal epithelium and surfactant is produced. This specialized region is generally separated from digestive portions of the gut by sphincters. GAB fishes tend to be facultative air breathers that use air breathing to supplement aquatic respiration in hypoxic waters. Some hindgut breathers may be continuous, but not obligate air breathers (obligate air breathers drown if denied access to air). Gut ABOs are generally used only for oxygen uptake; CO₂ elimination seems to occur via the gills and skin in all GAB fishes studied. Aerial ventilation in GAB fishes is driven primarily by oxygen partial pressure of the water (PO₂) and possibly also by metabolic demand. The effect of aerial ventilation on branchial ventilation and the cardiovascular system is complex and generalizations across taxa or ABO type are not currently possible. Blood from GAB fishes generally has a low blood oxygen partial pressure that half saturates haemoglobin (p50) with a very low erythrocytic nucleoside triphosphate concentration [NTP]. GAB behaviour in nature depends on the social and ecological context of the animal as well as on physiological factors. © 2014 The Fisheries Society of the British Isles.

ACES: An Enabling Technology for Next Generation Space Transportation

NASA Astrophysics Data System (ADS)

Crocker, Andrew M.; Wuerl, Adam M.; Andrews, Jason E.; Andrews, Dana G.

2004-02-01

Andrews Space has developed the ``Alchemist'' Air Collection and Enrichment System (ACES), a dual-mode propulsion system that enables safe, economical launch systems that take off and land horizontally. Alchemist generates liquid oxygen through separation of atmospheric air using the refrigeration capacity of liquid hydrogen. The key benefit of Alchemist is that it minimizes vehicle takeoff weight. All internal and NASA-funded activities have shown that ACES, previously proposed for hypersonic combined cycle RLVs, is a higher payoff, lower-risk technology if LOX generation is performed while the vehicle cruises subsonically. Andrews Space has developed the Alchemist concept from a small system study to viable Next Generation launch system technology, conducting not only feasibility studies but also related hardware tests, and it has planned a detailed risk reduction program which employs an experienced, proven contractor team. Andrews also has participated in preliminary studies of an evolvable Next Generation vehicle architecture-enabled by Alchemist ACES-which could meet civil, military, and commercial space requirements within two decades.

Light and oxygenic photosynthesis: energy dissipation as a protection mechanism against photo-oxidation

PubMed Central

Szabó, Ildikó; Bergantino, Elisabetta; Giacometti, Giorgio Mario

2005-01-01

Efficient photosynthesis is of fundamental importance for plant survival and fitness. However, in oxygenic photosynthesis, the complex apparatus responsible for the conversion of light into chemical energy is susceptible to photodamage. Oxygenic photosynthetic organisms have therefore evolved several protective mechanisms to deal with light energy. Rapidly inducible non-photochemical quenching (NPQ) is a short-term response by which plants and eukaryotic algae dissipate excitation energy as heat. This review focuses on recent advances in the elucidation of the molecular mechanisms underlying this protective quenching pathway in higher plants. PMID:15995679

Pilot Plant Makes Oxygen Difluoride

NASA Technical Reports Server (NTRS)

Humphrey, Marshall F.; Lawton, Emil A.

1989-01-01

Pilot plant makes oxygen difluoride highly-energetic, space-storable oxidizer not made commercially. Designed to handle reactants, product, and byproduct, most of which highly reactive, corrosive, and toxic. Oxygen difluoride evolves continuously from reactor containing potassium hydroxide in water at 10 degree C. Collection tanks alternated; one filled while other drained to storage cylinder. Excess OF2 and F2 dissipated in combustion of charcoal in burn barrel. Toxic byproduct, potassium fluoride, reacted with calcium hydroxide to form nontoxic calcium fluoride and to regenerate potassium hydroxide. Equipment processes toxic, difficult-to-make substance efficiently and safely.

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qinghua; He, Xu; Shi, Jinan

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Atomic-resolution imaging of electrically induced oxygen vacancy migration and phase transformation in SrCoO 2.5-σ

DOE PAGES

Zhang, Qinghua; He, Xu; Shi, Jinan; ...

2017-07-24

Oxygen ion transport is the key issue in redox processes. Visualizing the process of oxygen ion migration with atomic resolution is highly desirable for designing novel devices such as oxidation catalysts, oxygen permeation membranes, and solid oxide fuel cells. We show the process of electrically induced oxygen migration and subsequent reconstructive structural transformation in a SrCoO 2.5-σ film by scanning transmission electron microscopy. We find that the extraction of oxygen from every second SrO layer occurs gradually under an electrical bias; beyond a critical voltage, the brownmillerite units collapse abruptly and evolve into a periodic nano-twined phase with a highmore » c/a ratio and distorted tetrahedra. These results show that oxygen vacancy rows are not only natural oxygen diffusion channels, but also preferred sites for the induced oxygen vacancies. These direct experimental results of oxygen migration may provide a common mechanism for the electrically induced structural evolution of oxides.« less

Life cycle impacts of manufacturing redwood decking in Northern California

Treesearch

Richard D. Bergman; Elaine Oneil; Ivan L. Eastin; Han-Sup Han

2014-01-01

Awareness of the environmental footprint of building construction and use has led to increasing interest in green building. Defining a green building is an evolving process with life cycle inventory and life cycle impact assessment (LCIA) emerging as key tools in that evolution and definition process. This study used LCIA to determine the environmental footprint...

Physical activity when riding an electric assisted bicycle.

PubMed

Berntsen, Sveinung; Malnes, Lena; Langåker, Aleksander; Bere, Elling

2017-04-26

The objectives of the present study were to compare time spent cycling, exercise intensity, and time spent in moderate- (MPA) and vigorous intensity physical activity (VPA) when cycling on an E-bike and a conventional bicycle on two "cycling-to-work" routes with differences in topography, defined as a hilly and a flat route. Eight adults (23-54 years, two women) cycled outdoors on a conventional bicycle and an E-bike, on a flat (8.2 km) and a hilly (7.1 km) route, resulting in 32 journeys. Duration, elevation, and oxygen consumption were recorded using a portable oxygen analyser with GPS. A maximal cardiorespiratory fitness test was performed on a cycle ergometer. Resting metabolic rate was obtained by indirect calorimetry with a canopy hood. The participants spent less time (median (IQR)) cycling on the E-bike compared with the conventional bicycle, on both the hilly (18.8 (4.9) vs. 26.3 (6.4) minutes) and the flat (20.0 (2.9) vs. 23.8 (1.8) minutes) routes. Lower exercise intensity was observed with the E-bike compared with the conventional bicycle, both on the hilly (50 (18) vs. 60 (22) % of maximal oxygen uptake) and the flat (52 (19) vs. 55 (12) % of maximal oxygen uptake) routes. In both cycling modes, most time was spent in MVPA (92-99%). However, fewer minutes were spent in MVPA with the E-bike than the conventional bicycle, for both the hilly (26% lower) and the flat (17% lower) routes. Cycling on the E-bike also resulted in 35 and 15% fewer minutes in vigorous intensity, respectively on the hilly and flat routes. Cycling on the E-bike resulted in lower trip duration and exercise intensity, compared with the conventional bicycle. However, most of the time was spent in MVPA. This suggests that changing the commuting mode from car to E-bike will significantly increase levels of physical activity while commuting.

JavaGenes: Evolving Graphs with Crossover

NASA Technical Reports Server (NTRS)

Globus, Al; Atsatt, Sean; Lawton, John; Wipke, Todd

2000-01-01

Genetic algorithms usually use string or tree representations. We have developed a novel crossover operator for a directed and undirected graph representation, and used this operator to evolve molecules and circuits. Unlike strings or trees, a single point in the representation cannot divide every possible graph into two parts, because graphs may contain cycles. Thus, the crossover operator is non-trivial. A steady-state, tournament selection genetic algorithm code (JavaGenes) was written to implement and test the graph crossover operator. All runs were executed by cycle-scavagging on networked workstations using the Condor batch processing system. The JavaGenes code has evolved pharmaceutical drug molecules and simple digital circuits. Results to date suggest that JavaGenes can evolve moderate sized drug molecules and very small circuits in reasonable time. The algorithm has greater difficulty with somewhat larger circuits, suggesting that directed graphs (circuits) are more difficult to evolve than undirected graphs (molecules), although necessary differences in the crossover operator may also explain the results. In principle, JavaGenes should be able to evolve other graph-representable systems, such as transportation networks, metabolic pathways, and computer networks. However, large graphs evolve significantly slower than smaller graphs, presumably because the space-of-all-graphs explodes combinatorially with graph size. Since the representation strongly affects genetic algorithm performance, adding graphs to the evolutionary programmer's bag-of-tricks should be beneficial. Also, since graph evolution operates directly on the phenotype, the genotype-phenotype translation step, common in genetic algorithm work, is eliminated.

Optical fiber-mediated photosynthesis for enhanced subsurface oxygen delivery.

PubMed

Lanzarini-Lopes, Mariana; Delgado, Anca G; Guo, Yuanming; Dahlen, Paul; Westerhoff, Paul

2018-03-01

Remediation of polluted groundwater often requires oxygen delivery into subsurface to sustain aerobic bacteria. Air sparging or injection of oxygen containing solutions (e.g., hydrogen peroxide) into the subsurface are common. In this study visible light was delivered into the subsurface using radially emitting optical fibers. Phototrophic organisms grew near the optical fiber in a saturated sand column. When applying light in on-off cycles, dissolved oxygen (DO) varied from super saturation levels of >15 mg DO/L in presence of light to under-saturation (<5 mg DO/L) in absence of light. Non-photosynthetic bacteria dominated at longer radial distances from the fiber, presumably supported by soluble microbial products produced by the photosynthetic microorganisms. The dissolved oxygen variations alter redox condition changes in response to light demonstrate the potential to biologically deliver oxygen into the subsurface and support a diverse microbial community. The ability to deliver oxygen and modulate redox conditions on diurnal cycles using solar light may provide a sustainable, long term strategy for increasing dissolved oxygen levels in subsurface environments and maintaining diverse biological communities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of continuous and intermittent bouts of isocaloric cycling and running exercise on excess postexercise oxygen consumption.

PubMed

Cunha, Felipe A; Midgley, Adrian W; McNaughton, Lars R; Farinatti, Paulo T V

2016-02-01

The purpose of this study was to investigate excess postexercise oxygen consumption (EPOC) induced by isocaloric bouts of continuous and intermittent running and cycling exercise. This was a counterbalanced randomized cross-over study. Ten healthy men, aged 23-34yr, performed six bouts of exercise: (a) two maximal cardiopulmonary exercise tests for running and cycling to determine exercise modality-specific peak oxygen uptake (VO2peak); and (b) four isocaloric exercise bouts (two continuous bouts expending 400kcal and two intermittent bouts split into 2×200kcal) performed at 75% of the running and cycling oxygen uptake reserve. Exercise bouts were separated by 72h and performed in a randomized, counter-balanced order. The VO2 was monitored for 60-min postexercise and for 60-min during a control non-exercise day. The VO2 was significantly greater in all exercise conditions compared to the control session (P<0.001). The combined magnitude of the EPOC from the two intermittent bouts was significantly greater than that of the continuous cycling (mean difference=3.5L, P=0.001) and running (mean difference=6.4L, P<0.001). The exercise modality had a significant effect on net EPOC, where running elicited a higher net EPOC than cycling (mean difference=2.2L, P<0.001). Intermittent exercise increased the EPOC compared to a continuous exercise bout of equivalent energy expenditure. Furthermore, the magnitude of EPOC was influenced by exercise modality, with the greatest EPOC occurring with isocaloric exercise involving larger muscle mass (i.e., treadmill running vs. cycling). Copyright © 2015 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

The interplay between estuarine transport and biogeochemical processes in determining the nutrient conditions in bottom layers of non-tidal Gulf of Finland

NASA Astrophysics Data System (ADS)

Kõuts, Mariliis; Raudsepp, Urmas; Maljutenko, Ilja

2017-04-01

In coastal areas, especially estuaries, spatial distribution and seasonal cycling of chemical and biological variables is largely determined by local biogeochemical processes and water transport of different properties. In tidal estuaries, however, biogeochemical processes are affected by tides as frequent water exchange alters nutrient and oxygen concentrations. In wide and deep non-tidal estuary-type marginal seas spatial distribution and seasonal cycling are determined by the mixture of water transport and local biogeochemistry. The Baltic Sea is a stratified water basin where halocline divides the water column into two parts: upper layer, which is horizontally uniform in terms of distribution of chemical and biological parameters, and has clear seasonal cycle; and bottom part, where nutrient and oxygen dynamics is more complex. There water transport and sediment-water interface fluxes play a major role. Our prime focus is the Gulf of Finland in the Baltic Sea. It is a wide, non-tidal and stratified sub-basin known for its high nutrient concentrations and severe oxygen deficiency in summer. We modelled the Baltic Sea (including Gulf of Finland) using ERGOM, a biogeochemical model coupled with circulation model GETM. Seasonal cycling and water circulation were observed with a 40-year simulation from 1966 to 2006. Our results show that in shallow areas above halocline the seasonal cycle of phytoplankton, nutrients and oxygen concentrations is uniform in space. Water circulation does not create inhomogeneous distribution pattern of biogeochemical parameters and their seasonal cycle. The circulation in the Gulf of Finland is strongly modulated by the seasonality of estuarine transport. Below the halocline saline low-oxygen and nutrient-rich water is transported from the open Baltic Proper to the Gulf of Finland in spring and early summer. This results in the highest nutrient concentrations and the poorest oxygen conditions by the end of August. In the shallow area nutrients have high concentrations in March-April before the spring bloom of diatoms starts. Low oxygen and nutrient concentrations are observed at the end of August. There is a qualitative difference of nutrient dynamics between shallow and deep layers but quantification of the role of transport and local biogeochemical processes is still challenging.

Theory of chemical bonds in metalloenzymes XXI. Possible mechanisms of water oxidation in oxygen evolving complex of photosystem II

NASA Astrophysics Data System (ADS)

Yamaguchi, Kizashi; Shoji, Mitsuo; Isobe, Hiroshi; Yamanaka, Shusuke; Kawakami, Takashi; Yamada, Satoru; Katouda, Michio; Nakajima, Takahito

2018-03-01

Possible mechanisms for water cleavage in oxygen evolving complex (OEC) of photosystem II (PSII) have been investigated based on broken-symmetry (BS) hybrid DFT (HDFT)/def2 TZVP calculations in combination with available XRD, XFEL, EXAFS, XES and EPR results. The BS HDFT and the experimental results have provided basic concepts for understanding of chemical bonds of the CaMn4O5 cluster in the catalytic site of OEC of PSII for elucidation of the mechanism of photosynthetic water cleavage. Scope and applicability of the hybrid DFT (HDFT) methods have been examined in relation to relative stabilities of possible nine intermediates such as Mn-hydroxide, Mn-oxo, Mn-peroxo, Mn-superoxo, etc., in order to understand the O-O (O-OH) bond formation in the S3 and/or S4 states of OEC of PSII. The relative stabilities among these intermediates are variable, depending on the weight of the Hartree-Fock exchange term of HDFT. The Mn-hydroxide, Mn-oxo and Mn-superoxo intermediates are found to be preferable in the weak, intermediate and strong electron correlation regimes, respectively. Recent different serial femtosecond X-ray (SFX) results in the S3 state are investigated based on the proposed basic concepts under the assumption of different water-insertion steps for water cleavage in the Kok cycle. The observation of water insertion in the S3 state is compatible with previous large-scale QM/MM results and previous theoretical proposal for the chemical equilibrium mechanism in the S3 state . On the other hand, the no detection of water insertion in the S3 state based on other SFX results is consistent with previous proposal of the O-OH (or O-O) bond formation in the S4 state . Radical coupling and non-adiabatic one-electron transfer (NA-OET) mechanisms for the OO-bond formation are examined using the energy diagrams by QM calculations and by QM(UB3LYP)/MM calculations . Possible reaction pathways for the O-O and O-OH bond formations are also investigated based on two water-inlet pathways for oxygen evolution in OEC of PSII. Future perspectives are discussed in relation to post HDFT calculations of the energy diagrams for elucidation of the mechanism of water oxidation in OEC of PSII.

Deconvoluting lung evolution: from phenotypes to gene regulatory networks

PubMed Central

Torday, John S.; Rehan, Virender K.; Hicks, James W.; Wang, Tobias; Maina, John; Weibel, Ewald R.; Hsia, Connie C.W.; Sommer, Ralf J.; Perry, Steven F.

2007-01-01

Speakers in this symposium presented examples of respiratory regulation that broadly illustrate principles of evolution from whole organ to genes. The swim bladder and lungs of aquatic and terrestrial organisms arose independently from a common primordial “respiratory pharynx” but not from each other. Pathways of lung evolution are similar between crocodiles and birds but a low compliance of mammalian lung may have driven the development of the diaphragm to permit lung inflation during inspiration. To meet the high oxygen demands of flight, bird lungs have evolved separate gas exchange and pump components to achieve unidirectional ventilation and minimize dead space. The process of “screening” (removal of oxygen from inspired air prior to entering the terminal units) reduces effective alveolar oxygen tension and potentially explains why nonathletic large mammals possess greater pulmonary diffusing capacities than required by their oxygen consumption. The “primitive” central admixture of oxygenated and deoxygenated blood in the incompletely divided reptilian heart is actually co-regulated with other autonomic cardiopulmonary responses to provide flexible control of arterial oxygen tension independent of ventilation as well as a unique mechanism for adjusting metabolic rate. Some of the most ancient oxygen-sensing molecules, i.e., hypoxia-inducible factor-1alpha and erythropoietin, are up-regulated during mammalian lung development and growth under apparently normoxic conditions, suggesting functional evolution. Normal alveolarization requires pleiotropic growth factors acting via highly conserved cell–cell signal transduction, e.g., parathyroid hormone-related protein transducing at least partly through the Wingless/int pathway. The latter regulates morphogenesis from nematode to mammal. If there is commonality among these diverse respiratory processes, it is that all levels of organization, from molecular signaling to structure to function, co-evolve progressively, and optimize an existing gas-exchange framework. PMID:20607138

RE-EXAMINING HIGH ABUNDANCE SLOAN DIGITAL SKY SURVEY MASS-METALLICITY OUTLIERS: HIGH N/O, EVOLVED WOLF-RAYET GALAXIES?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, Danielle A.; Skillman, Evan D.; Marble, Andrew R., E-mail: berg@astro.umn.edu, E-mail: skillman@astro.umn.edu, E-mail: amarble@nso.edu

We present new MMT spectroscopic observations of four dwarf galaxies representative of a larger sample observed by the Sloan Digital Sky Survey and identified by Peeples et al. as low-mass, high oxygen abundance outliers from the mass-metallicity relation. Peeples showed that these four objects (with metallicity estimates of 8.5 {<=} 12 + log(O/H) {<=} 8.8) have oxygen abundance offsets of 0.4-0.6 dex from the M{sub B} luminosity-metallicity relation. Our new observations extend the wavelength coverage to include the [O II] {lambda}{lambda}3726, 3729 doublet, which adds leverage in oxygen abundance estimates and allows measurements of N/O ratios. All four spectra aremore » low excitation, with relatively high N/O ratios (N/O {approx}> 0.10), each of which tend to bias estimates based on strong emission lines toward high oxygen abundances. These spectra all fall in a regime where the 'standard' strong-line methods for metallicity determinations are not well calibrated either empirically or by photoionization modeling. By comparing our spectra directly to photoionization models, we estimate oxygen abundances in the range of 7.9 {<=} 12 + log (O/H) {<=} 8.4, consistent with the scatter of the mass-metallicity relation. We discuss the physical nature of these galaxies that leads to their unusual spectra (and previous classification as outliers), finding their low excitation, elevated N/O, and strong Balmer absorption are consistent with the properties expected from galaxies evolving past the 'Wolf-Rayet galaxy' phase. We compare our results to the 'main' sample of Peeples and conclude that they are outliers primarily due to enrichment of nitrogen relative to oxygen and not due to unusually high oxygen abundances for their masses or luminosities.« less

Oxygen and oxidative stress in the perinatal period.

PubMed

Torres-Cuevas, Isabel; Parra-Llorca, Anna; Sánchez-Illana, Angel; Nuñez-Ramiro, Antonio; Kuligowski, Julia; Cháfer-Pericás, Consuelo; Cernada, María; Escobar, Justo; Vento, Máximo

2017-08-01

Fetal life evolves in a hypoxic environment. Changes in the oxygen content in utero caused by conditions such as pre-eclampsia or type I diabetes or by oxygen supplementation to the mother lead to increased free radical production and correlate with perinatal outcomes. In the fetal-to-neonatal transition asphyxia is characterized by intermittent periods of hypoxia ischemia that may evolve to hypoxic ischemic encephalopathy associated with neurocognitive, motor, and neurosensorial impairment. Free radicals generated upon reoxygenation may notably increase brain damage. Hence, clinical trials have shown that the use of 100% oxygen given with positive pressure in the airways of the newborn infant during resuscitation causes more oxidative stress than using air, and increases mortality. Preterm infants are endowed with an immature lung and antioxidant system. Clinical stabilization of preterm infants after birth frequently requires positive pressure ventilation with a gas admixture that contains oxygen to achieve a normal heart rate and arterial oxygen saturation. In randomized controlled trials the use high oxygen concentrations (90% to 100%) has caused more oxidative stress and clinical complications that the use of lower oxygen concentrations (30-60%). A correlation between the amount of oxygen received during resuscitation and the level of biomarkers of oxidative stress and clinical outcomes was established. Thus, based on clinical outcomes and analytical results of oxidative stress biomarkers relevant changes were introduced in the resuscitation policies. However, it should be underscored that analysis of oxidative stress biomarkers in biofluids has only been used in experimental and clinical research but not in clinical routine. The complexity of the technical procedures, lack of automation, and cost of these determinations have hindered the routine use of biomarkers in the clinical setting. Overcoming these technical and economical difficulties constitutes a challenge for the immediate future since accurate evaluation of oxidative stress would contribute to improve the quality of care of our neonatal patients. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Cryptic oxygen cycling in anoxic marine zones.

PubMed

Garcia-Robledo, Emilio; Padilla, Cory C; Aldunate, Montserrat; Stewart, Frank J; Ulloa, Osvaldo; Paulmier, Aurélien; Gregori, Gerald; Revsbech, Niels Peter

2017-08-01

Oxygen availability drives changes in microbial diversity and biogeochemical cycling between the aerobic surface layer and the anaerobic core in nitrite-rich anoxic marine zones (AMZs), which constitute huge oxygen-depleted regions in the tropical oceans. The current paradigm is that primary production and nitrification within the oxic surface layer fuel anaerobic processes in the anoxic core of AMZs, where 30-50% of global marine nitrogen loss takes place. Here we demonstrate that oxygenic photosynthesis in the secondary chlorophyll maximum (SCM) releases significant amounts of O 2 to the otherwise anoxic environment. The SCM, commonly found within AMZs, was dominated by the picocyanobacteria Prochlorococcus spp. Free O 2 levels in this layer were, however, undetectable by conventional techniques, reflecting a tight coupling between O 2 production and consumption by aerobic processes under apparent anoxic conditions. Transcriptomic analysis of the microbial community in the seemingly anoxic SCM revealed the enhanced expression of genes for aerobic processes, such as nitrite oxidation. The rates of gross O 2 production and carbon fixation in the SCM were found to be similar to those reported for nitrite oxidation, as well as for anaerobic dissimilatory nitrate reduction and sulfate reduction, suggesting a significant effect of local oxygenic photosynthesis on Pacific AMZ biogeochemical cycling.

Development of an Advanced Respirometer for Experimental Studies of Benthic Rate Processes

NASA Astrophysics Data System (ADS)

Barry, J. P.; Buck, K. R.; Okuda, C.; Risi, M.; Parker, M.; Levesque, C.

2005-05-01

Rates of carbon remineralization and nutrient cycling by seafloor biotic assemblages are influenced by the availability of organic material, temperature, and oxygen availability, among other factors. The relative importance of various factors in controlling carbon cycling by the sediment community is poorly constrained, in part by technological limits on experiments that evaluate independently the effects of these factors. We have developed an advanced respiration chamber system capable of repeated rate measurements during a single deployment, with added capabilities for manipulating conditions within replicate chambers to test hypotheses concerning biogeochemical cycling by the benthos. The ROV-deployed respiration system has 12 syringes for tracer injection or sample withdrawal from 3 respiration chambers, pH, oxygen, and temperature sensors, stirring paddles, and a recirculation pump. The pump system is used to flush each chamber at preprogrammed intervals or oxygen tensions. Areas of investigation that are enabled by the system include the effects various factors on benthic oxygen consumptions (e.g. hypercapnia (elevated CO2), acidosis, ambient oxygen availability, temperature, organic carbon availability), rates of nutrient regeneration by the benthos in response to organic enrichments (labile and refractory organic carbon), time lags in carbon uptake and trophic pathways in responses to organic enrichment.

SBR treatment of tank truck cleaning wastewater: sludge characteristics, chemical and ecotoxicological effluent quality.

PubMed

Caluwé, Michel; Dobbeleers, Thomas; Daens, Dominique; Geuens, Luc; Blust, Ronny; Dries, Jan

2017-08-02

A lab-scale activated sludge sequencing batch reactor (SBR) was used to treat tank truck cleaning (TTC) wastewater with different operational strategies (identified as different stages). The first stage was an adaptation period for the seed sludge that originated from a continuous fed industrial plant treating TTC wastewater. The first stage was followed by a dynamic reactor operation based on the oxygen uptake rate (OUR). Thirdly, dynamic SBR control based on OUR treated a daily changing influent. Lastly, the reactor was operated with a gradually shortened fixed cycle. During operation, sludge settling evolved from nearly no settling to good settling sludge in 16 days. The sludge volume index improved from 200 to 70 mL gMLSS -1 in 16 days and remained stable during the whole reactor operation. The average soluble chemical oxygen demand (sCOD) removal varied from 87.0% to 91.3% in the different stages while significant differences in the food to mass ratio were observed, varying from 0.11 (stage I) to 0.37 kgCOD.(kgMLVSS day) -1 (stage III). Effluent toxicity measurements were performed with Aliivibrio fischeri, Daphnia magna and Pseudokirchneriella subcapitata. Low sensitivity of Aliivibrio was observed. A few samples were acutely toxic for Daphnia; 50% of the tested effluent samples showed an inhibition of 100% for Pseudokirchneriella.

Multiple sample characterization of coals and other substances by controlled-atmosphere programmed temperature oxidation

DOEpatents

LaCount, Robert B.

1993-01-01

A furnace with two hot zones holds multiple analysis tubes. Each tube has a separable sample-packing section positioned in the first hot zone and a catalyst-packing section positioned in the second hot zone. A mass flow controller is connected to an inlet of each sample tube, and gas is supplied to the mass flow controller. Oxygen is supplied through a mass flow controller to each tube to either or both of an inlet of the first tube and an intermediate portion between the tube sections to intermingle with and oxidize the entrained gases evolved from the sample. Oxidation of those gases is completed in the catalyst in each second tube section. A thermocouple within a sample reduces furnace temperature when an exothermic condition is sensed within the sample. Oxidized gases flow from outlets of the tubes to individual gas cells. The cells are sequentially aligned with an infrared detector, which senses the composition and quantities of the gas components. Each elongated cell is tapered inward toward the center from cell windows at the ends. Volume is reduced from a conventional cell, while permitting maximum interaction of gas with the light beam. Reduced volume and angulation of the cell inlets provide rapid purgings of the cell, providing shorter cycles between detections. For coal and other high molecular weight samples, from 50% to 100% oxygen is introduced to the tubes.

Closed-Cycle Hydrogen-Oxygen Regenerative Fuel Cell at the NASA Glenn Research Center-An Update

NASA Technical Reports Server (NTRS)

Bents, David J.; Chang, Bei-Jiann; Johnson, Donald W.; Garcia, Christopher P.

2008-01-01

The closed cycle hydrogen-oxygen proton exchange membrane (PEM) regenerative fuel cell (RFC) at the NASA Glenn Research Center has demonstrated multiple back-to-back contiguous cycles at rated power and round-trip efficiencies up to 52 percent. It is the first fully closed cycle RFC ever demonstrated. (The entire system is sealed; nothing enters or escapes the system other than electrical power and heat.) During fiscal year fiscal year (FY) FY06 to FY07, the system s numerous modifications and internal improvements focused on reducing parasitic power, heat loss, and noise signature; increasing its functionality as an unattended automated energy storage device; and in-service reliability.

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

DOE PAGES

Bang, Suhee; Lee, Yong -Min; Hong, Seungwoo; ...

2014-09-14

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η 2:η 2-O 2)–M n+ (M n+ = Sr 2+, Ca 2+, Zn 2+, Lu 3+, Y 3+ and Sc 3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca 2+ and Sr 2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities ofmore » complexes formed with stronger Lewis acidities were found to be markedly different. In conclusion, complexes that contain Ca 2+ or Sr 2+ ions were oxidized by an electron acceptor to release O 2, whereas the release of O 2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca 2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.« less

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

PubMed Central

Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

2014-01-01

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η2:η2-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. Complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. We discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex. PMID:25242490

Structural Coupling of Extrinsic Proteins with the Oxygen-Evolving Center in Photosystem II

PubMed Central

Ifuku, Kentaro; Noguchi, Takumi

2016-01-01

Photosystem II (PSII), which catalyzes photosynthetic water oxidation, is composed of more than 20 subunits, including membrane-intrinsic and -extrinsic proteins. The PSII extrinsic proteins shield the catalytic Mn4CaO5 cluster from the outside bulk solution and enhance binding of inorganic cofactors, such as Ca2+ and Cl-, in the oxygen-evolving center (OEC) of PSII. Among PSII extrinsic proteins, PsbO is commonly found in all oxygenic organisms, while PsbP and PsbQ are specific to higher plants and green algae, and PsbU, PsbV, CyanoQ, and CyanoP exist in cyanobacteria. In addition, red algae and diatoms have unique PSII extrinsic proteins, such as PsbQ′ and Psb31, suggesting functional divergence during evolution. Recent studies with reconstitution experiments combined with Fourier transform infrared spectroscopy have revealed how the individual PSII extrinsic proteins affect the structure and function of the OEC in different organisms. In this review, we summarize our recent results and discuss changes that have occurred in the structural coupling of extrinsic proteins with the OEC during evolutionary history. PMID:26904056

A Case Study in CAD Design Automation

ERIC Educational Resources Information Center

Lowe, Andrew G.; Hartman, Nathan W.

2011-01-01

Computer-aided design (CAD) software and other product life-cycle management (PLM) tools have become ubiquitous in industry during the past 20 years. Over this time they have continuously evolved, becoming programs with enormous capabilities, but the companies that use them have not evolved their design practices at the same rate. Due to the…

Metal oxidation states in biological water splitting† †Electronic supplementary information (ESI) available: Additional methodological details and discussion, Tables S1–S10, Fig. S1–S16, spin populations, parameters of optimized structures, experimental details and analysis of 55Mn ENDOR at 2.5 K, analysis of calculated Mn K pre-edge XAS, discussion of reduced S states. See DOI: 10.1039/c4sc03720k Click here for additional data file.

PubMed Central

Krewald, Vera; Retegan, Marius; Cox, Nicholas; Messinger, Johannes; Lubitz, Wolfgang; DeBeer, Serena; Neese, Frank

2015-01-01

A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five Si states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster. PMID:29308133

Peak oxygen uptake in a sprint interval testing protocol vs. maximal oxygen uptake in an incremental testing protocol and their relationship with cross-country mountain biking performance.

PubMed

Hebisz, Rafał; Hebisz, Paulina; Zatoń, Marek; Michalik, Kamil

2017-04-01

In the literature, the exercise capacity of cyclists is typically assessed using incremental and endurance exercise tests. The aim of the present study was to confirm whether peak oxygen uptake (V̇O 2peak ) attained in a sprint interval testing protocol correlates with cycling performance, and whether it corresponds to maximal oxygen uptake (V̇O 2max ) determined by an incremental testing protocol. A sample of 28 trained mountain bike cyclists executed 3 performance tests: (i) incremental testing protocol (ITP) in which the participant cycled to volitional exhaustion, (ii) sprint interval testing protocol (SITP) composed of four 30 s maximal intensity cycling bouts interspersed with 90 s recovery periods, (iii) competition in a simulated mountain biking race. Oxygen uptake, pulmonary ventilation, work, and power output were measured during the ITP and SITP with postexercise blood lactate and hydrogen ion concentrations collected. Race times were recorded. No significant inter-individual differences were observed in regards to any of the ITP-associated variables. However, 9 individuals presented significantly increased oxygen uptake, pulmonary ventilation, and work output in the SITP compared with the remaining cyclists. In addition, in this group of 9 cyclists, oxygen uptake in SITP was significantly higher than in ITP. After the simulated race, this group of 9 cyclists achieved significantly better competition times (99.5 ± 5.2 min) than the other cyclists (110.5 ± 6.7 min). We conclude that mountain bike cyclists who demonstrate higher peak oxygen uptake in a sprint interval testing protocol than maximal oxygen uptake attained in an incremental testing protocol demonstrate superior competitive performance.

Understanding the Differences in the Nitrogen Cycle in the Seasonal Low-Oxygen Zone in the Saanich Inlet of Vancouver Island, British Columbia.

NASA Astrophysics Data System (ADS)

Wood, C.; Forbes, M. S.

2017-12-01

Ocean Oxygen Deficient Zones (ODZs) are found in specific regions around the globe. ODZs generally form from upwelling of nutrient-rich waters, which drives oxygen consumption. The Saanich Inlet in British Columbia, Canada, is an ODZ, as it experiences oxygen consumption due to its unique topography, where a sill at its entrance prevents mixing with the surrounding ocean for much of the year. Due to this, oxygen and nitrate are consumed but not replenished until winter and spring, when the higher-velocity oxygen rich waters cycle the water. Our objective is to understand this cycle via the δ15N and δ18O analysis of NO3 and NO2 isotopes in conjunction with concentration data. Samples were collected bi-monthly over a 7-month period between September 2016 to March 2017. Initial oxygen readings were conducted on the cruise, as well as conductivity, depth, and position. Over the summer, data has been collected and analyzed on most NO3 samples from the trip. Oxygen levels generally decreased with depth, with a dramatic change (200 to 10 µM) at approximately 100 m. Concentrations of NO3 follow a similar trend, decreasing at this point from 20 to less than 5 µM. Conversely, δ15N and δ18O become more enriched at these lower depths, reaching values of 40.97 ‰ and 31.86 ‰, respectively. During the first half of the sample period, some detectable concentrations of NO2 were identified. In the second half, NO2 was not identified. This preliminary data suggests the presence of denitrification occurring in the inlet throughout the fall and winter period and is most likely a combination of water column and sedimentary denitrification. Data towards the end of the sampling period suggest possible completion of denitrification and a likely influx of nutrient rich waters. We will apply this data set to continue to analyze and explore the effects of low oxygen levels on these nitrogen cycle processes with further analysis of isotope data, to further understand the relationships.

Phase transformations of siderite ore by the thermomagnetic analysis data

NASA Astrophysics Data System (ADS)

Ponomar, V. P.; Dudchenko, N. O.; Brik, A. B.

2017-02-01

Thermal decomposition of Bakal siderite ore (that consists of magnesium siderite and ankerite traces) was investigated by thermomagnetic analysis. Thermomagnetic analysis was carried-out using laboratory-built facility that allows automatic registration of sample magnetization with the temperature (heating/cooling rate was 65°/min, maximum temperature 650 °C) at low- and high-oxygen content. Curie temperature gradually decreases with each next cycles of heating/cooling at low-oxygen content. Curie temperature decrease after 2nd cycle of heating/cooling at high-oxygen content and do not change with next cycles. Final Curie temperature for both modes was 320 °C. Saturation magnetization of obtained samples increases up to 20 Am2/kg. The final product of phase transformation at both modes was magnesioferrite. It was shown that intermediate phase of thermal decomposition of Bakal siderite ore was magnesiowustite.

Dual-cycle ergometry as an exercise modality during prebreathe with 100 percent oxygen

NASA Technical Reports Server (NTRS)

Heaps, Cristine L.; Fischer, Michele D.; Webb, James T.

1994-01-01

In an effort to reduce prebreathe time requirements prior to extravehicular activities and high-altitude flights, a combined arm and leg exercise task proposes to enhance denitrogenation by incorporation of both upper and lower body musculature at a moderately high work intensity during prebreathe with 100% oxygen. Preliminary findings indicated peak oxygen consumption (VO2peak) levels attained on the dual-cycle ergometer do not differ significantly from those levels attained on the treadmill. Eight male subjects were exercised to VO2peak using leg-only cycle ergometry and dual-cycle ergometry on separate days. Preliminary data during dual-cycle ergometry showed arm work equaling 30% of the leg workrate at each stage of the incremental test resulted in arm fatigue in several subjects and a reduced VO2peak compared to dual-cycle ergometry with arm work at 20%. Thus, the 20% workrate was used during the dual-cycle VO2peak trial. On a third experimental day, subjects performed a 10 minute exercise test at a workrate required to elicit 75% of VO2peak for each subject on the dual-cycle ergometer. Blood lactate response to the exercise was monitored as an objective measure of fatigue. Peak VO2 levels attained on the leg-only and the dual-cycle ergometry tasks were not significantly different. Blood lactate levels were significantly elevated following the dual-cycle ergometry at 75% VO2peak. However, lactate levels show the expected rate of decline during recovery and, as demonstrated in the literature, should return to baseline levels within 30 minutes following exercise cessation. Thus, dual-cycle ergometry at 75% VO2peak appears to be a valid exercise for use during prebreathe and should not contribute to fatigue during subsequent EVA's.

Hydrogen-Oxygen PEM Regenerative Fuel Cell Development at the NASA Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.; Scullin, Vincent J.; Chang, Bei-Jiann; Johnson, Donald W.; Garcia, Christoher P.; Jakupca, Ian J.

2005-01-01

The closed-cycle hydrogen-oxygen PEM regenerative fuel cell (RFC) at the NASA Glenn Research Center has successfully demonstrated closed cycle operation at rated power for multiple charge-discharge cycles. During charge cycle the RFC has absorbed input electrical power simulating a solar day cycle ranging from zero to 15 kWe peak, and delivered steady 5 kWe output power for periods exceeding 8 hr. Orderly transitions from charge to discharge mode, and return to charging after full discharge, have been accomplished without incident. Continuing test operations focus on: (1) Increasing the number of contiguous uninterrupted charge discharge cycles; (2) Increasing the performance envelope boundaries; (3) Operating the RFC as an energy storage device on a regular basis; (4) Gaining operational experience leading to development of fully automated operation; and (5) Developing instrumentation and in situ fluid sampling strategies to monitor health and anticipate breakdowns.

Evolution of flexible non-photochemical quenching mechanisms that regulate light harvesting in oxygenic photosynthesis.

PubMed

Niyogi, Krishna K; Truong, Thuy B

2013-06-01

All photosynthetic organisms need to regulate light harvesting for photoprotection. Three types of flexible non-photochemical quenching (NPQ) mechanisms have been characterized in oxygenic photosynthetic cyanobacteria, algae, and plants: OCP-, LHCSR-, and PSBS-dependent NPQ. OCP-dependent NPQ likely evolved first, to quench excess excitation in the phycobilisome (PB) antenna of cyanobacteria. During evolution of eukaryotic algae, PBs were lost in the green and secondary red plastid lineages, while three-helix light-harvesting complex (LHC) antenna proteins diversified, including LHCSR proteins that function in dissipating excess energy rather than light harvesting. PSBS, an independently evolved member of the LHC protein superfamily, seems to have appeared exclusively in the green lineage, acquired a function as a pH sensor that turns on NPQ, and eventually replaced LHCSR in vascular plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rechargeable aqueous lithium-air batteries with an auxiliary electrode for the oxygen evolution

NASA Astrophysics Data System (ADS)

Sunahiro, S.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

2014-09-01

A rechargeable aqueous lithium-air cell with a third auxiliary electrode for the oxygen evolution reaction was developed. The cell consists of a lithium metal anode, a lithium conducting solid electrolyte of Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12, a carbon black oxygen reduction air electrode, a RuO2 oxygen evolution electrode, and a saturated aqueous solution of LiOH with 10 M LiCl. The cell was successfully operated for several cycles at 0.64 mA cm-2 and 25 °C under air, where the capacity of air electrode was 2000 mAh gcathod-1. The cell performance was degraded gradually by cycling under open air. The degradation was reduced under CO2-free air and pure oxygen. The specific energy density was calculated to be 810 Wh kg-1 from the weight of water, lithium, oxygen, and carbon in the air electrode.

Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

NASA Astrophysics Data System (ADS)

Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent

2011-02-01

The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

Evaluation of atomic oxygen resistant protective coatings for fiberglass-epoxy composites in LEO

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Paulsen, Phillip E.; Brady, Joyce A.

1989-01-01

Fiberglass-epoxy composite masts are the prime structural members for the Space Station Freedom solar array. At the altitude where Space Station Freedom will operate, atomic oxygen atoms are the most predominant species. Atomic oxygen is highly reactive and has been shown to oxidize organic and some metallic materials. Tests with random and directed atomic oxygen exposure have shown that the epoxy is removed from the composite exposing brittle glass fibers which could be easily removed from the surface where they could contaminate Space Station Freedom Systems. Protection or fiber containment systems; inorganic based paints, aluminum braid, and a metal coating; were evaluated for resistance to atomic oxygen, vacuum ultraviolet radiation, thermal cycling, and mechanical flexing. All appeared to protect well against atomic oxygen and provide fiber containment except for the single aluminum braid covering. UV radiation resistance was acceptable and in general, thermal cycling and flexure had little to no effect on the mass loss rate for most coatings.

Net production of oxygen in the subtropical ocean.

PubMed

Riser, Stephen C; Johnson, Kenneth S

2008-01-17

The question of whether the plankton communities in low-nutrient regions of the ocean, comprising 80% of the global ocean surface area, are net producers or consumers of oxygen and fixed carbon is a key uncertainty in the global carbon cycle. Direct measurements in bottle experiments indicate net oxygen consumption in the sunlit zone, whereas geochemical evidence suggests that the upper ocean is a net source of oxygen. One possible resolution to this conflict is that primary production in the gyres is episodic and thus difficult to observe: in this model, oligotrophic regions would be net consumers of oxygen during most of the year, but strong, brief events with high primary production rates might produce enough fixed carbon and dissolved oxygen to yield net production as an average over the annual cycle. Here we examine the balance of oxygen production over three years at sites in the North and South Pacific subtropical gyres using the new technique of oxygen sensors deployed on profiling floats. We find that mixing events during early winter homogenize the upper water column and cause low oxygen concentrations. Oxygen then increases below the mixed layer at a nearly constant rate that is similar to independent measures of net community production. This continuous oxygen increase is consistent with an ecosystem that is a net producer of fixed carbon (net autotrophic) throughout the year, with episodic events not required to sustain positive oxygen production.

Oxygen isotope constraints on the sulfur cycle over the past 10 million years.

PubMed

Turchyn, Alexandra V; Schrag, Daniel P

2004-03-26

Oxygen isotopes in marine sulfate (delta18O(SO4)) measured in marine barite show variability over the past 10 million years, including a 5 per mil decrease during the Plio-Pleistocene, with near-constant values during the Miocene that are slightly enriched over the modern ocean. A numerical model suggests that sea level fluctuations during Plio-Pleistocene glacial cycles affected the sulfur cycle by reducing the area of continental shelves and increasing the oxidative weathering of pyrite. The data also require that sulfate concentrations were 10 to 20% lower in the late Miocene than today.

SPECTRAL EVOLUTION OF ANOMALOUS COSMIC RAYS AT VOYAGER 1 BEYOND THE TERMINATION SHOCK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senanayake, U. K.; Florinski, V.; Cummings, A. C.

When the Voyager 1 spacecraft crossed the termination shock (TS) on 2004 December 16, the energy spectra of anomalous cosmic rays (ACRs) could not have been produced by steady-state diffusive shock acceleration. However, over the next few years, in the declining phase of the solar cycle, the spectra began to evolve into the expected power-law profile. Observations at the shock led to a broad range of alternative theories for ACR acceleration. In spite of that, in this work we show that the observations could be explained by assuming ACRs are accelerated at the TS. In this paper, we propose thatmore » the solar cycle had an important effect on the unrolling of the spectra in the heliosheath. To investigate the spectral evolution of ACRs, a magnetohydrodynamic background model with stationary solar-wind inner boundary conditions was used to model the transport of helium and oxygen ions. We used a backward-in-time stochastic integration technique where phase-space trajectories are integrated until the so-called “injection energy” is reached. Our simulation results were compared with Voyager 1 observations using three different diffusion models. It is shown that the spectral evolution of ACRs in the heliosheath at Voyager 1 could be explained by an increase in the source strength and an enhancement in diffusion as a result of a decrease of the turbulent correlation length in the declining phase of the solar cycle. At the same time, drift effects seem to have had a smaller effect on the evolution of the spectra.« less

Molecular water oxidation mechanisms followed by transition metals: state of the art.

PubMed

Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

2014-02-18

One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.

Po2 cycling protects diaphragm function during reoxygenation via ROS, Akt, ERK, and mitochondrial channels.

PubMed

Zuo, Li; Pannell, Benjamin K; Re, Anthony T; Best, Thomas M; Wagner, Peter D

2015-12-01

Po2 cycling, often referred to as intermittent hypoxia, involves exposing tissues to brief cycles of low oxygen environments immediately followed by hyperoxic conditions. After experiencing long-term hypoxia, muscle can be damaged during the subsequent reintroduction of oxygen, which leads to muscle dysfunction via reperfusion injury. The protective effect and mechanism behind Po2 cycling in skeletal muscle during reoxygenation have yet to be fully elucidated. We hypothesize that Po2 cycling effectively increases muscle fatigue resistance through reactive oxygen species (ROS), protein kinase B (Akt), extracellular signal-regulated kinase (ERK), and certain mitochondrial channels during reoxygenation. Using a dihydrofluorescein fluorescent probe, we detected the production of ROS in mouse diaphragmatic skeletal muscle in real time under confocal microscopy. Muscles treated with Po2 cycling displayed significantly attenuated ROS levels (n = 5; P < 0.001) as well as enhanced force generation compared with controls during reperfusion (n = 7; P < 0.05). We also used inhibitors for signaling molecules or membrane channels such as ROS, Akt, ERK, as well as chemical stimulators to close mitochondrial ATP-sensitive potassium channel (KATP) or open mitochondrial permeability transition pore (mPTP). All these blockers or stimulators abolished improved muscle function with Po2 cycling treatment. This current investigation has discovered a correlation between KATP and mPTP and the Po2 cycling pathway in diaphragmatic skeletal muscle. Thus we have identified a unique signaling pathway that may involve ROS, Akt, ERK, and mitochondrial channels responsible for Po2 cycling protection during reoxygenation conditions in the diaphragm. Copyright © 2015 the American Physiological Society.

How diverse is the oxygen consumption during the life cycle of the pelagic tunicate Dolioletta gegenbauri?

NASA Astrophysics Data System (ADS)

Koester, M.; Paffenhofer, G. A.

2016-02-01

The goal of our study was to study the intraspecies physiological diversity of different life stages of the pelagic tunicate Dolioletta gegenbauri (Tunicata, Thaliacea) that occur intermittently in high abundances on the shelf off the southeastern US. The complex life cycle of this species starts with solitary oozooids that develop to nurses with colonies of feeding trophozooids and phorozooids. As the latter mature they produce clusters of gonozooids. As oxygen consumption is a good physiological indicator for metabolic expenditures, we quantified the oxygen consumption of different zooids of D. gegenbauri (nurses, phorozooids and gonozooids) at environmental conditions. Oxygen consumption rates were determined from changes in oxygen concentration that were monitored non-invasively and continuously by an innovative sensor system in time-series-experiments. Specific oxygen consumption rates varied considerably and were related to moving activity, feeding behaviour, biomass, and growth of different life stages of doliolids. The results of our study will advance our understanding of variability in oxygen consumption of different stages of doliolid development due to their specific ecological role.

Metagenomic analysis of nitrogen and methane cycling in the Arabian Sea oxygen minimum zone.

PubMed

Lüke, Claudia; Speth, Daan R; Kox, Martine A R; Villanueva, Laura; Jetten, Mike S M

2016-01-01

Oxygen minimum zones (OMZ) are areas in the global ocean where oxygen concentrations drop to below one percent. Low oxygen concentrations allow alternative respiration with nitrate and nitrite as electron acceptor to become prevalent in these areas, making them main contributors to oceanic nitrogen loss. The contribution of anammox and denitrification to nitrogen loss seems to vary in different OMZs. In the Arabian Sea, both processes were reported. Here, we performed a metagenomics study of the upper and core zone of the Arabian Sea OMZ, to provide a comprehensive overview of the genetic potential for nitrogen and methane cycling. We propose that aerobic ammonium oxidation is carried out by a diverse community of Thaumarchaeota in the upper zone of the OMZ, whereas a low diversity of Scalindua-like anammox bacteria contribute significantly to nitrogen loss in the core zone. Aerobic nitrite oxidation in the OMZ seems to be performed by Nitrospina spp. and a novel lineage of nitrite oxidizing organisms that is present in roughly equal abundance as Nitrospina. Dissimilatory nitrate reduction to ammonia (DNRA) can be carried out by yet unknown microorganisms harbouring a divergent nrfA gene. The metagenomes do not provide conclusive evidence for active methane cycling; however, a low abundance of novel alkane monooxygenase diversity was detected. Taken together, our approach confirmed the genomic potential for an active nitrogen cycle in the Arabian Sea and allowed detection of hitherto overlooked lineages of carbon and nitrogen cycle bacteria.

Metagenomic analysis of nitrogen and methane cycling in the Arabian Sea oxygen minimum zone

PubMed Central

Kox, Martine A.R.; Villanueva, Laura; Jetten, Mike S.M.

2016-01-01

Oxygen minimum zones (OMZ) are areas in the global ocean where oxygen concentrations drop to below one percent. Low oxygen concentrations allow alternative respiration with nitrate and nitrite as electron acceptor to become prevalent in these areas, making them main contributors to oceanic nitrogen loss. The contribution of anammox and denitrification to nitrogen loss seems to vary in different OMZs. In the Arabian Sea, both processes were reported. Here, we performed a metagenomics study of the upper and core zone of the Arabian Sea OMZ, to provide a comprehensive overview of the genetic potential for nitrogen and methane cycling. We propose that aerobic ammonium oxidation is carried out by a diverse community of Thaumarchaeota in the upper zone of the OMZ, whereas a low diversity of Scalindua-like anammox bacteria contribute significantly to nitrogen loss in the core zone. Aerobic nitrite oxidation in the OMZ seems to be performed by Nitrospina spp. and a novel lineage of nitrite oxidizing organisms that is present in roughly equal abundance as Nitrospina. Dissimilatory nitrate reduction to ammonia (DNRA) can be carried out by yet unknown microorganisms harbouring a divergent nrfA gene. The metagenomes do not provide conclusive evidence for active methane cycling; however, a low abundance of novel alkane monooxygenase diversity was detected. Taken together, our approach confirmed the genomic potential for an active nitrogen cycle in the Arabian Sea and allowed detection of hitherto overlooked lineages of carbon and nitrogen cycle bacteria. PMID:27077014

On optima: the case of myoglobin-facilitated oxygen diffusion.

PubMed

Wittenberg, Jonathan B

2007-08-15

The process of myoglobin/leghemoglobin-facilitated oxygen diffusion is adapted to function in different environments in diverse organisms. We enquire how the functional parameters of the process are optimized in particular organisms. The ligand-binding properties of the proteins, myoglobin and plant symbiotic hemoglobins, we discover, suggest that they have been adapted under genetic selection pressure for optimal performance. Since carrier-mediated oxygen transport has probably evolved independantly many times, adaptation of diverse proteins for a common functionality exemplifies the process of convergent evolution. The progenitor proteins may be built on the myoglobin scaffold or may be very different.

The development of a non-cryogenic nitrogen/oxygen supply system. [using hydrazine/water electrolysis

NASA Technical Reports Server (NTRS)

Greenough, B. M.; Mahan, R. E.

1974-01-01

A hydrazine/water electrolysis process system module design was fabricated and tested to demonstrate component and module performance. This module is capable of providing both the metabolic oxygen for crew needs and the oxygen and nitrogen for spacecraft leak makeup. The component designs evolved through previous R and D efforts, and were fabricated and tested individually and then were assembled into a complete module which was successfully tested for 1000 hours to demonstrate integration of the individual components. A survey was made of hydrazine sensor technology and a cell math model was derived.

Evolved Populations of Shigella flexneri Phage Sf6 Acquire Large Deletions, Altered Genomic Architecture, and Faster Life Cycles.

PubMed

Dover, John A; Burmeister, Alita R; Molineux, Ian J; Parent, Kristin N

2016-09-19

Genomic architecture is the framework within which genes and regulatory elements evolve and where specific constructs may constrain or potentiate particular adaptations. One such construct is evident in phages that use a headful packaging strategy that results in progeny phage heads packaged with DNA until full rather than encapsidating a simple unit-length genome. Here, we investigate the evolution of the headful packaging phage Sf6 in response to barriers that impede efficient phage adsorption to the host cell. Ten replicate populations evolved faster Sf6 life cycles by parallel mutations found in a phage lysis gene and/or by large, 1.2- to 4.0-kb deletions that remove a mobile genetic IS911 element present in the ancestral phage genome. The fastest life cycles were found in phages that acquired both mutations. No mutations were found in genes encoding phage structural proteins, which were a priori expected from the experimental design that imposed a challenge for phage adsorption by using a Shigella flexneri host lacking receptors preferred by Sf6. We used DNA sequencing, molecular approaches, and physiological experiments on 82 clonal isolates taken from all 10 populations to reveal the genetic basis of the faster Sf6 life cycle. The majority of our isolates acquired deletions in the phage genome. Our results suggest that deletions are adaptive and can influence the duration of the phage life cycle while acting in conjunction with other lysis time-determining point mutations. © The Author 2016. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries

NASA Astrophysics Data System (ADS)

Zhang, Jian; Luan, Yanping; Lyu, Zhiyang; Wang, Liangjun; Xu, Leilei; Yuan, Kaidi; Pan, Feng; Lai, Min; Liu, Zhaolin; Chen, Wei

2015-09-01

A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery.A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02983j

Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery.

PubMed

Wandt, Johannes; Jakes, Peter; Granwehr, Josef; Gasteiger, Hubert A; Eichel, Rüdiger-A

2016-06-06

Aprotic lithium-oxygen (Li-O2 ) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen ((1) Δg ) is formed upon Li2 O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time- and voltage-resolved in operando EPR spectroscopy in a purpose-built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O2 cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of a lunar oxygen production plant

NASA Technical Reports Server (NTRS)

Radhakrishnan, Ramalingam

1990-01-01

To achieve permanent human presence and activity on the moon, oxygen is required for both life support and propulsion. Lunar oxygen production using resources existing on the moon will reduce or eliminate the need to transport liquid oxygen from earth. In addition, the co-products of oxygen production will provide metals, structural ceramics, and other volatile compounds. This will enable development of even greater self-sufficiency as the lunar outpost evolves. Ilmenite is the most abundant metal-oxide mineral in the lunar regolith. A process involving the reaction of ilmenite with hydrogen at 1000 C to produce water, followed by the electrolysis of this water to provide oxygen and recycle the hydrogen has been explored. The objective of this 1990 Summer Faculty Project was to design a lunar oxygen-production plant to provide 5 metric tons of liquid oxygen per year from lunar soil. The results of this study describe the size and mass of the equipment, the power needs, feedstock quantity and the engineering details of the plant.

Singlet oxygen generator for a solar powered chemically pumped iodine laser

NASA Technical Reports Server (NTRS)

Busch, G. E.

1984-01-01

The potential of solid phase endoperoxides as a means to produce single-delta oxygen in the gas phase in concentrations useful to chemical oxygen-iodine lasers was investigated. The 1,4 - endoperoxide of ethyl 3- (4-methyl - 1-naphthyl) propanoate was deposited over an indium-oxide layer on a glass plate. Single-delta oxygen was released from the endoperoxide upon heating the organic film by means of an electrical discharge through the conductive indium oxide coating. The evolution of singlet-delta oxygen was determined by measuring the dimol emission signal at 634 nm. Comparison of the measured signal with an analytic model leads to two main conclusions: virtually all the oxygen being evolved is in the singlet-delta state and in the gas phase, and there is no significant quenching other than energy pooling on the time scale of the experiment (approximately 10 msec). The use of solid phase endoperoxide as a singlet-delta oxygen generator for an oxygen-iodine laser appears promising.

Center for Thin Film Studies

DTIC Science & Technology

1988-10-31

techniques, and to investigate the simultaneous use of ion bombardment and substrate cooling for production of low-loss, stable ZnS material. 7 0.14 q(a) N...films indicate that even implanted argon is firmly embedded and shows no tendency to evolve. When the ions are reactive (e.g., oxygen or nitrogen ...oxygen ions can result in very good oxide layers. Nitrogen is another compound-forming gas which lacks sufficient reactivity to have been a useful

Lunar Water Resource Demonstration (LWRD)

NASA Technical Reports Server (NTRS)

Muscatello, Anthony C.

2009-01-01

Lunar Water Resource Demonstration (LWRD) is part of RESOLVE (Regolith and Environment Science & Oxygen and Lunar Volatile Extraction). RESOLVE is an ISRU ground demonstration: (1) A rover to explore a permanently shadowed crater at the south or north pole of the Moon (2) Drill core samples down to 1 meter (3) Heat the core samples to 150C (4) Analyze gases and capture water and/or hydrogen evolved (5) Use hydrogen reduction to extract oxygen from regolith

Deep reactive ion etching of 4H-SiC via cyclic SF6/O2 segments

NASA Astrophysics Data System (ADS)

Luna, Lunet E.; Tadjer, Marko J.; Anderson, Travis J.; Imhoff, Eugene A.; Hobart, Karl D.; Kub, Fritz J.

2017-10-01

Cycles of inductively coupled SF6/O2 plasma with low (9%) and high (90%) oxygen content etch segments are used to produce up to 46.6 µm-deep trenches with 5.5 µm-wide openings in single-crystalline 4H-SiC substrates. The low oxygen content segment serves to etch deep in SiC whereas the high oxygen content segment serves to etch SiC at a slower rate, targeting carbon-rich residues on the surface as the combination of carbon-rich and fluorinated residues impact sidewall profile. The cycles work in concert to etch past 30 µm at an etch rate of ~0.26 µm min-1 near room temperature, while maintaining close to vertical sidewalls, high aspect ratio, and high mask selectivity. In addition, power ramps during the low oxygen content segment is used to produce a 1:1 ratio of mask opening to trench bottom width. The effect of process parameters such as cycle time and backside substrate cooling on etch depth and micromasking of the electroplated nickel etch mask are investigated.

BIOREMEDIATION OF PETROLEUM HYDROCARBONS: A FLEXIBLE VARIABLE SPEED TECHNOLOGY

EPA Science Inventory

The bioremediation of petroleum hydrocarbons has evolved into a number of different processes. These processes include in-situ aquifer bioremediation, bioventing, biosparging, passive bioremediation with oxygen release compounds, and intrinsic bioremediation. Although often viewe...

[Effect of different oxygen concentrations on biological properties of bone marrow hematopoietic stem cells of mice].

PubMed

Ma, Yi-Ran; Ren, Si-Hua; He, Yu-Xin; Wang, Lin-Lin; Jin, Li; Hao, Yi-Wen

2012-10-01

This study purposed to investigate the effects of different oxygen concentrations and reactive oxygen species (ROS) on the biological characteristics of hematopoietic stem cells (HSC) and their possible mechanisms through simulating oxygen environment to which the peripheral blood HSC are subjected in peripheral blood HSCT. The proliferation ability, cell cycle, directed differentiation ability, ROS level and hematopoietic reconstitution ability of Lin(-)c-kit(+)Sca-1(+) BMHSC were detected by using in vitro amplification test, directional differentiation test, cell cycle analysis, ROS assay and transplantation of Lin(-)c-kit(+)Sca-1(+) HSC from sublethally irradiated mice respectively. The results showed that oxygen concentrations lower than normal oxygen concentration, especially in hypoxic oxygen environment, could reduce ROS generation and amplify more primitive CD34(+)AC133(+) HSC and active CD34(+) HSC, and maintain more stem cells in the G(0)/G(1) phase, which is more helpful to the growth of CFU-S and viability of mice. At the same time, BMHSC exposed to normal oxygen level or inconstant and greatly changed oxygen concentrations could produce a high level of ROS, and the above-mentioned features and functional indicators are relatively low. It is concluded that ROS levels of HSC in BMHSCT are closely related with the oxygen concentration surrounding the cells and its stability. Low oxygen concentration and antioxidant intervention are helpful to transplantation of BMHSC.

AC impedance study of degradation of porous nickel battery electrodes

NASA Technical Reports Server (NTRS)

Lenhart, Stephen J.; Macdonald, D. D.; Pound, B. G.

1987-01-01

AC impedance spectra of porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (nonporous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low.

Testing the fidelity of laminations as a proxy for oxygen concentration in the Bering Sea over millennial to orbital timescales

NASA Astrophysics Data System (ADS)

Black, A. E.; Baranow, N.; Amdur, S.; Cook, M. S.

2017-12-01

Ocean circulation and biological productivity play an important role in the climate system through their contribution to global heat transport and air-sea exchange of CO­2. Oceanic oxygen concentration provides insight to ocean circulation and biological productivity. Sediment laminations provide a valuable proxy for local oceanic oxygen concentration. Many sediment cores from the Pacific Ocean are laminated from the last deglaciation, but previous studies have not provided an in-depth examination of laminations over many glacial and interglacial (G/IG) cycles. Typically, studies to date that consider bioturbation as a proxy for oxygen concentration have only considered one sediment core from a site, leaving ambiguity as to whether laminations faithfully record local oxygen levels. With sediment cores from three different holes (A, C, D) on the northern Bering Slope from IODP site U1345 (1008m), we investigate how faithfully laminations record oxygen concentration. We assign a bioturbation index from 1 to 4 for 1-cm intervals for the cores from each of the three holes and align the holes based on physical properties data. We find that the bioturbation is relatively consistent (within one bioturbation unit) between holes, suggesting that laminations may be a faithful, if not perfect, proxy for local oxygen concentration. After examining laminations from a complete hole, representing over 500,000 years, there seems to be no consistent pattern of laminations during the past five glacial cycles, suggesting there is no consistent pattern to oxygen concentration during glacial periods in the northern Bering Slope. Thus, hypotheses on ocean circulation and productivity in the northern Bering Sea from the last deglaciation may not apply to previous G/IG cycles.

Cryptic oxygen cycling in anoxic marine zones

PubMed Central

Padilla, Cory C.; Stewart, Frank J.; Ulloa, Osvaldo; Paulmier, Aurélien; Gregori, Gerald; Revsbech, Niels Peter

2017-01-01

Oxygen availability drives changes in microbial diversity and biogeochemical cycling between the aerobic surface layer and the anaerobic core in nitrite-rich anoxic marine zones (AMZs), which constitute huge oxygen-depleted regions in the tropical oceans. The current paradigm is that primary production and nitrification within the oxic surface layer fuel anaerobic processes in the anoxic core of AMZs, where 30–50% of global marine nitrogen loss takes place. Here we demonstrate that oxygenic photosynthesis in the secondary chlorophyll maximum (SCM) releases significant amounts of O2 to the otherwise anoxic environment. The SCM, commonly found within AMZs, was dominated by the picocyanobacteria Prochlorococcus spp. Free O2 levels in this layer were, however, undetectable by conventional techniques, reflecting a tight coupling between O2 production and consumption by aerobic processes under apparent anoxic conditions. Transcriptomic analysis of the microbial community in the seemingly anoxic SCM revealed the enhanced expression of genes for aerobic processes, such as nitrite oxidation. The rates of gross O2 production and carbon fixation in the SCM were found to be similar to those reported for nitrite oxidation, as well as for anaerobic dissimilatory nitrate reduction and sulfate reduction, suggesting a significant effect of local oxygenic photosynthesis on Pacific AMZ biogeochemical cycling. PMID:28716941

Simplex turbopump design

NASA Technical Reports Server (NTRS)

Marsh, Matt; Cowan, Penny

1994-01-01

Turbomachinery used in liquid rocket engines typically are composed of complex geometries made from high strength-to-weight super alloys and have long design and fabrication cycle times (3 to 5 years). A simple, low-cost turbopump is being designed in-house to demonstrate the ability to reduce the overall cost to $500K and compress life cycle time to 18 months. The simplex turbopump was designed to provide a discharge pressure of 1500 psia of liquid oxygen at 90 lbm/s. The turbine will be powered by gaseous oxygen. This eliminates the need for an inter-propellant seal typically required to separate the fuel-rich turbine gases from the liquid oxygen pump components. Materials used in the turbine flow paths will utilize existing characterized metals at 800 deg R that are compatible with a warm oxygen environment. This turbopump design would be suitable for integration with a 40 K pound thrust hybrid motor that provides warm oxygen from a tapped-off location to power the turbine. The preliminary and detailed analysis was completed in a year by a multiple discipline, concurrent engineering team. Manpower, schedule, and cost data were tracked during the process for a comparison to the initial goal. The Simplex hardware is the procurement cycle with the expectation of the first test to occur approximately 1.5 months behind the original schedule goal.

Oxidation of platinum nickel nanowires to improve durability of oxygen-reducing electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Dameron, Arrelaine; ...

2016-01-12

In this study, the impact of heat treating platinum-coated nickel (Pt-Ni) nanowires in oxygen is examined to determine the effect on oxygen reduction (ORR) activity and durability. Pt-Ni nanowires exhibit promising ORR mass activities (3 times greater than Pt nanoparticles, 1.5 times greater than U.S. Department of Energy target) both before and after potential cycling for all but the highest annealing temperatures explored. The annealing of Pt-Ni nanowires in oxygen with increasing temperature is found to reduce surface area and ORR activity in comparison to the untreated material, but also reduces activity losses following durability testing. Following potential cycling, unannealedmore » Pt-Ni nanowires show significant losses in surface area (23%) and specific activity (18%) while Pt-Ni nanowires annealed at 200°C show modest increases in surface area (2%) and specific activity (6%) after potential cycling. Increasing annealing temperatures also show a clear trend of decreasing Ni dissolution rates. While oxygen annealing has shown the ability to improve durability of Pt-Ni nanowires, significant Ni dissolution was observed in all samples and suggests oxide passivation while showing promise for improved durability, when employed by itself is insufficient to prevent all contamination concerns involving Ni dissolution.« less

Placing an upper limit on cryptic marine sulphur cycling.

PubMed

Johnston, D T; Gill, B C; Masterson, A; Beirne, E; Casciotti, K L; Knapp, A N; Berelson, W

2014-09-25

A quantitative understanding of sources and sinks of fixed nitrogen in low-oxygen waters is required to explain the role of oxygen-minimum zones (OMZs) in controlling the fixed nitrogen inventory of the global ocean. Apparent imbalances in geochemical nitrogen budgets have spurred numerous studies to measure the contributions of heterotrophic and autotrophic N2-producing metabolisms (denitrification and anaerobic ammonia oxidation, respectively). Recently, 'cryptic' sulphur cycling was proposed as a partial solution to the fundamental biogeochemical problem of closing marine fixed-nitrogen budgets in intensely oxygen-deficient regions. The degree to which the cryptic sulphur cycle can fuel a loss of fixed nitrogen in the modern ocean requires the quantification of sulphur recycling in OMZ settings. Here we provide a new constraint for OMZ sulphate reduction based on isotopic profiles of oxygen ((18)O/(16)O) and sulphur ((33)S/(32)S, (34)S/(32)S) in seawater sulphate through oxygenated open-ocean and OMZ-bearing water columns. When coupled with observations and models of sulphate isotope dynamics and data-constrained model estimates of OMZ water-mass residence time, we find that previous estimates for sulphur-driven remineralization and loss of fixed nitrogen from the oceans are near the upper limit for what is possible given in situ sulphate isotope data.

Flake-like oxygen-deficient lithium vanadium oxides as a high ionic and electronic conductive cathode material for high-power Li-ion battery

NASA Astrophysics Data System (ADS)

Li, Jing-quan; Han, Chong; Jing, Mao-xiang; Yang, Hua; Shen, Xiang-qian; Qin, Shi-biao

2018-06-01

Low electronic and ionic conductivity for LiV3O8 cathode material could lead to poor cycling stability and rate capability, which are considered as the main restraint for its application in Li-ion battery. A novel flake-like LiV3O7.9 material modified by high ionic and electronic conductive Li0.3V2O5/C was fabricated via electrospinning and controlled thermal sintering processes. This oxygen-deficient LiV3O7.9/Li0.3V2O5-C composite electrode sintered at 500 °C exhibits improved rate and cycle stability. The electrode possesses a retention capacity of 151.9mAh/g after 500 cycles at 5C and 84.8mAh/g after 1000 cycles at 10C, respectively. The improvement of the electrochemical performance could be attributed to the synergistic effects of flake-like morphology, oxygen-deficiency and surface modification of Li0.3V2O5/C, which increase the ionic and electronic conductivity of LiV3O8.

Li-air batteries: Importance of singlet oxygen

NASA Astrophysics Data System (ADS)

Luntz, Alan C.; McCloskey, Bryan D.

2017-04-01

The deployment of Li-air batteries is hindered by severe parasitic reactions during battery cycling. Now, the reactive singlet oxygen intermediate is shown to substantially contribute to electrode and electrolyte degradation.

Multicycle study on chemical-looping combustion of simulated coal gas with a CaSO{sub 4} oxygen carrier in a fluidized bed reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qilei Song; Rui Xiao; Zhongyi Deng

2008-11-15

The cyclic test of a CaSO{sub 4}-based oxygen carrier (natural anhydrite) in alternating reducing simulated coal gas and oxidizing conditions was performed at 950{degree}C in a fluidized bed reactor at atmospheric pressure. A high concentration of CO{sub 2} was obtained in the reduction. The H{sub 2} and CO conversions and CO{sub 2} yield increased initially and final decreased significantly. The release of SO{sub 2} and H{sub 2}S during the cyclic test was found to be responsible for the decrease of reactivity of a CaSO{sub 4} oxygen carrier. The oxygen carrier conversion after the reduction reaction decreased gradually in the cyclicmore » test. Through the comparison of mass-based reaction rates as a function of mass conversion at typical cycles, it was also evident that the reactivity of a CaSO{sub 4} oxygen carrier increased for the initial cycles but finally decreased after around 15 cycles. X-ray diffraction analysis revealed that the presence and intensity of the reduction sulfur species was in accordance with the results of gas conversion. The content of CaO was higher than expected, suggesting the formation of SO{sub 2} and H{sub 2}S during the cycles. Surface morphology analysis demonstrates that the natural anhydrite particle surface varied from impervious to porous after the cyclic test. It was also observed that the small grains on the surface of the oxygen carrier sintered in the cyclic tests. Energy-dispersive spectrum analysis also demonstrated the decrease of oxygen intensity after reduction, and CaO became the main component after the 20th oxidation. Pore structure analysis suggested that the particles agglomerated or sintered in the cyclic tests. The possible method for sulfur mitigation is proposed. Finally, some basic consideration on the design criteria of a CLC system for solid fuels using a CaSO{sub 4} oxygen carrier is discussed by the references and provides direction for future work. 49 refs., 10 figs., 5 tabs.« less

Assessment of the menstrual cycle upon total hemoglobin, water concentration, and oxygen saturation in the female breast

NASA Astrophysics Data System (ADS)

Jiang, Shudong; Pogue, Brian W.; Srinivasan, Subhadra; Soho, Sandra; Poplack, Steven P.; Tosteson, Tor D.; Paulsen, Keith D.

2003-07-01

Near-infrared imaging can be used in humans to characterize changes in breast tumor tissue by imaging total hemoglobin and water concentrations as well as oxygen saturation. In order to improve our understanding of these changes, we need to carefully quantify the range of variation possible in normal tissues for these parameters. In this study, the effect of the subject"s menstrual cycle was examined by imaging their breast at the follicular (7-14 days of the cycle) and secretory phases (21-28 days of the cycle), using our NIR tomographic system. In this system, a three layer patient interface is used to measure 3 planes along the breast from chest wall towards the nipple at 1cm increments. Seven volunteers in their 40s were observed for 2 menstrual cycles and all of these volunteers recently had normal mammograms (ACR 1) with heterogeneously dense breast composition. The results show that average total hemoglobin in the breast increased in many subjects between 0 to 15% from the follicular phase to secretory phase. Oxygen saturation and water concentration changes between these 2 parts of the cycle were between -6.5% to 12% for saturation and between -33% to 28% for water concentration. While the data averaged between subjects showed no significant change existed between phases, it was clear that individual subjects did exhibit changes in composition which were consistent from cycle to cycle. Understanding what leads to this heterogeneity between subjects will be an important factor in utilizing these measurements in clinical practice.

A study of QM/Langevin-MD simulation for oxygen-evolving center of photosystem II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uchida, Waka; Kimura, Yoshiro; Wakabayashi, Masamitsu

2013-12-10

We have performed three QM/Langevin-MD simulations for oxygen-evolving complex (OEC) and surrounding residues, which are different configurations of the oxidation numbers on Mn atoms in the Mn{sub 4}O{sub 5}Ca cluster. By analyzing these trajectories, we have observed sensitivity of the change to the configuration of Mn oxidation state on O atoms of carboxyl on three amino acids, Glu354, Ala344, and Glu333. The distances from Mn to O atoms in residues contacting with the Mn{sub 4}O{sub 5}Ca cluster were analyzed for the three trajectories. We found the good correlation of the distances among the simulations. However, the distances with Glu354, Ala344,more » and Glu333 have not shown the correlation. These residues can be sensitive index of the changes of Mn oxidation numbers.« less

Paracellular transport as a strategy for energy conservation by multicellular organisms?

PubMed

Yu, Alan S L

2017-04-03

Paracellular transport of solutes and water accompanies transcellular transport across epithelial barriers and together they serve to maintain internal body composition. However, whether paracellular transport is necessary and why it evolved is unknown. In this commentary I discuss our recent studies to address this question in the proximal tubule of the kidney. Paracellular reabsorption of sodium occurs in the proximal tubule and is mediated by claudin-2. However, deletion of claudin-2 in mice does not affect whole kidney sodium excretion because it can be completely compensated by downtream transcellular transport mechanisms. This occurs at the expense of increased oxygen consumption, tissue hypoxia and increased susceptibility to ischemic injury. It is concluded that paracellular transport acts as an energy saving mechanism to increase transport without consuming additional oxygen. It is speculated that this might be why paracellular transport evolved in leaky epithelia with high transport needs.

Paracellular transport as a strategy for energy conservation by multicellular organisms?

PubMed Central

Yu, Alan S. L.

2017-01-01

ABSTRACT Paracellular transport of solutes and water accompanies transcellular transport across epithelial barriers and together they serve to maintain internal body composition. However, whether paracellular transport is necessary and why it evolved is unknown. In this commentary I discuss our recent studies to address this question in the proximal tubule of the kidney. Paracellular reabsorption of sodium occurs in the proximal tubule and is mediated by claudin-2. However, deletion of claudin-2 in mice does not affect whole kidney sodium excretion because it can be completely compensated by downtream transcellular transport mechanisms. This occurs at the expense of increased oxygen consumption, tissue hypoxia and increased susceptibility to ischemic injury. It is concluded that paracellular transport acts as an energy saving mechanism to increase transport without consuming additional oxygen. It is speculated that this might be why paracellular transport evolved in leaky epithelia with high transport needs. PMID:28452575

Spectra from the IRS of Bright Oxygen-Rich Evolved Stars in the SMC

NASA Astrophysics Data System (ADS)

Kraemer, Kathleen E.; Sloan, Greg; Wood, Peter

2016-06-01

We have used Spitzer's Infrared Spectrograph (IRS) to obtain spectra of stars in the Small Magellanic Cloud (SMC). The targets were chosen from the Point Source Catalog of the Mid-Course Space Experiment (MSX), which detected the 243 brightest infrared sources in the SMC. Our SMC sample of oxygen-rich evolved stars shows more dust than found in previous samples, and the dust tends to be dominated by silicates, with little contribution from alumina. Both results may arise from the selection bias in the MSX sample and our sample toward more massive stars. Additionally, several sources show peculiar spectral features such as PAHs, crystalline silicates, or both carbon-rich and silicate features. The spectrum of one source, MSX SMC 145, is a combination of an ordinary AGB star and a background galaxy at z~0.16, rather than an OH/IR star as previously suggested.

Correlation between pH dependence of O2 evolution and sensitivity of Mn cations in the oxygen-evolving complex to exogenous reductants.

PubMed

Semin, Boris K; Davletshina, Lira N; Rubin, Andrei B

2015-08-01

Effects of pH, Ca(2+), and Cl(-) ions on the extraction of Mn cations from oxygen-evolving complex (OEC) in Ca-depleted photosystem II (PSII(-Ca)) by exogenous reductants hydroquinone (H2Q) and H2O2 were studied. Two of 4 Mn cations are released by H2Q and H2O2 at pHs 5.7, 6.5, and 7.5, and their extraction does not depend on the presence of Ca(2+) and Cl(-) ions. One of Mn cations ("resistant" Mn cation) cannot be extracted by H2Q and H2O2 at any pH. Extraction of 4th Mn ion ("flexible" Mn cation) is sensitive to pH, Ca(2+), and Cl(-). This Mn cation is released by reductants at pH 6.5 but not at pHs 5.7 and 7.5. A pH dependence curve of the oxygen-evolving activity in PSII(-Ca) membranes (in the presence of exogenous Ca(2+)) has a bell-shaped form with the maximum at pH 6.5. Thus, the increase in the resistance of flexible Mn cation in OEC to the action of reductants at acidic and alkaline pHs coincides with the decrease in oxygen evolution activity at these pHs. Exogenous Ca(2+) protects the extraction of flexible Mn cation at pH 6.5. High concentration of Cl(-) anions (100 mM) shifts the pH optimum of oxygen evolution to alkaline region (around pH 7.5), while the pH of flexible Mn extraction is also shifted to alkaline pH. This result suggests that flexible Mn cation plays a key role in the water-splitting reaction. The obtained results also demonstrate that only one Mn cation in Mn4 cluster is under strong control of calcium. The change in the flexible Mn cation resistance to exogenous reductants in the presence of Ca(2+) suggests that Ca(2+) can control the redox potential of this cation.

Morning-to-evening differences in oxygen uptake kinetics in short-duration cycling exercise.

PubMed

Brisswalter, Jeanick; Bieuzen, François; Giacomoni, Magali; Tricot, Véronique; Falgairette, Guy

2007-01-01

This study analyzed diurnal variations in oxygen (O(2)) uptake kinetics and efficiency during a moderate cycle ergometer exercise. Fourteen physically active diurnally active male subjects (age 23+/-5 yrs) not specifically trained at cycling first completed a test to determine their ventilatory threshold (T(vent)) and maximal oxygen consumption (VO(2max)); one week later, they completed four bouts of testing in the morning and evening in a random order, each separated by at least 24 h. For each period of the day (07:00-08:30 h and 19:00-20:30 h), subjects performed two bouts. Each bout was composed of a 5 min cycling exercise at 45 W, followed after 5 min rest by a 10 min cycling exercise at 80% of the power output associated with T(vent). Gas exchanges were analyzed breath-by-breath and fitted using a mono-exponential function. During moderate exercise, the time constant and amplitude of VO(2) kinetics were significantly higher in the morning compared to the evening. The net efficiency increased from the morning to evening (17.3+/-4 vs. 20.5+/-2%; p<0.05), and the variability of cycling cadence was greater during the morning than evening (+34%; p<0.05). These findings suggest that VO(2) responses are affected by the time of day and could be related to variability in muscle activity pattern.

Cuckoo Search Algorithm Based on Repeat-Cycle Asymptotic Self-Learning and Self-Evolving Disturbance for Function Optimization

PubMed Central

Wang, Jie-sheng; Li, Shu-xia; Song, Jiang-di

2015-01-01

In order to improve convergence velocity and optimization accuracy of the cuckoo search (CS) algorithm for solving the function optimization problems, a new improved cuckoo search algorithm based on the repeat-cycle asymptotic self-learning and self-evolving disturbance (RC-SSCS) is proposed. A disturbance operation is added into the algorithm by constructing a disturbance factor to make a more careful and thorough search near the bird's nests location. In order to select a reasonable repeat-cycled disturbance number, a further study on the choice of disturbance times is made. Finally, six typical test functions are adopted to carry out simulation experiments, meanwhile, compare algorithms of this paper with two typical swarm intelligence algorithms particle swarm optimization (PSO) algorithm and artificial bee colony (ABC) algorithm. The results show that the improved cuckoo search algorithm has better convergence velocity and optimization accuracy. PMID:26366164

Reactive Oxygen Species and NOX Enzymes Are Emerging as Key Players in Cutaneous Wound Repair

PubMed Central

Modarressi, Ali; Pittet-Cuénod, Brigitte

2017-01-01

Our understanding of the role of oxygen in cell physiology has evolved from its long-recognized importance as an essential factor in oxidative metabolism to its recognition as an important player in cell signaling. With regard to the latter, oxygen is needed for the generation of reactive oxygen species (ROS), which regulate a number of different cellular functions including differentiation, proliferation, apoptosis, migration, and contraction. Data specifically concerning the role of ROS-dependent signaling in cutaneous wound repair are very limited, especially regarding wound contraction. In this review we provide an overview of the current literature on the role of molecular and reactive oxygen in the physiology of wound repair as well as in the pathophysiology and therapy of chronic wounds, especially under ischemic and hyperglycemic conditions. PMID:29036938

Frozen-Plug Technique for Liquid-Oxygen Plumbing

NASA Technical Reports Server (NTRS)

McCaskey, C. E. " Mac" ; Lobmeyer, Dennis; Nagy, Zoltan; Peltzer, Rich

2005-01-01

A frozen-plug technique has been conceived as a means of temporarily blocking the flow of liquid oxygen or its vapor through a tube or pipe. The technique makes it possible to perform maintenance, repair, or other work on downstream parts of the cryogenic system in which the oxygen is used, without having to empty an upstream liquid-oxygen reservoir and, hence, without wasting the stored liquid oxygen and without subjecting the reservoir to the stresses of thermal cycling.

Laser-induced changes in intraretinal oxygen distribution in pigmented rabbits.

PubMed

Yu, Dao-Yi; Cringle, Stephen J; Su, Erning; Yu, Paula K; Humayun, Mark S; Dorin, Giorgio

2005-03-01

To make the first measurements of intraretinal oxygen distribution and consumption after laser photocoagulation of the retina and to compare the efficiency of micropulsed (MP) and continuous wave (CW) laser delivery in achieving an oxygen benefit in the treated area. Oxygen-sensitive microelectrodes were used to measure oxygen tension as a function of retinal depth before and after laser treatment in anesthetized, mechanically ventilated, Dutch Belted rabbits (n = 11). Laser lesions were created by using a range of power levels from an 810-nm diode laser coupled with an operating microscope delivery system. MP duty cycles of 5%, 10%, and 15% were compared with CW delivery in each eye. Sufficient power levels of both the CW and MP laser reduced outer retinal oxygen consumption and increased oxygen level within the retina. At these power levels, which correlated with funduscopically visible lesions, there was histologically visible damage to the RPE and photoreceptors. Retinal damage was energy dependent but short-duty-cycle MP delivery was more selective in terms of retinal cell damage, with a wider safety range in comparison with CW delivery. The relationship between laser power level and mode of delivery and the resultant changes in oxygen metabolism and oxygen level in the retina was determined. Only partial destruction of RPE and photoreceptors is necessary, to produce a measurable oxygen benefit in the treated area of retina.

Unusual Reactivity of the Martian Soil: Oxygen Release Upon Humidification

NASA Technical Reports Server (NTRS)

Yen, A. S.

2002-01-01

Recent lab results show that oxygen evolves from superoxide-coated mineral grains upon exposure to water vapor. This observation is additional support of the hypothesis that UV-generated O2 is responsible for the reactivity of the martian soil. Discussion of current NASA research opportunities, status of various programs within the Solar System Exploration Division, and employment opportunities within NASA Headquarters to support these programs. Additional information is contained in the original extended abstract.

Multi-yolk-shell SnO2/Co3Sn2@C Nanocubes with High Initial Coulombic Efficiency and Oxygen Reutilization for Lithium Storage.

PubMed

Su, Liwei; Xu, Yawei; Xie, Jian; Wang, Lianbang; Wang, Yuanhao

2016-12-28

The challenging problems of SnO 2 anode material for lithium ion batteries are the poor electronic conductivity and the low oxygen reutilization due to the irreversibility of Li 2 O generated in the initial discharge leading to a theoretical initial Coulombic efficiency (ICE) of only 52.4%. Different from these strategies, this work proposes a novel strategy to level up the oxygen reutilization in SnO 2 by introducing Co 3 Sn 2 nanoalloys which can release Co atoms to reversibly react with Li 2 O instead. According to this protocol, multi-yolk-shell SnO 2 /Co 3 Sn 2 @C nanocubes are designed and successfully prepared using hollow CoSn(OH) 6 nanocubes as precursors followed a hydrothermal carbon coating and calcination treatment. The unique multi-yolk-shell nanostructure offers adequate breathing space for the volumetric deformation during long-term cycling. Moreover, the removal of Li 2 O allows a high electronic conductivity and resultant rate performance. As a result, the efficient reutilization of oxygen enables a high ICE of 71.7% and a reversible capacity of 1003 mA h g -1 after 200 cycles at 100 mA g -1 . Cyclic voltammetry, cycling performance at different voltage windows, and X-ray photoelectron spectroscopy confirm the proposed mechanism. This strategy employing oxygen-poor metals or alloys provides a novel approach to enhance the oxygen reutilization in SnO 2 for higher reversibility.

Decompression Sickness During Simulated Low Pressure Exposure is Increased with Mild Ambulation Exercise

NASA Technical Reports Server (NTRS)

Pollock, N. W.; Natoli, M. J.; Martina, S. D.; Conkin, J.; Wessel, J. H., III; Gernhardt, M. L.

2016-01-01

Musculoskeletal activity accelerates inert gas elimination during oxygen breathing prior to decompression (prebreathe), but may also promote bubble formation (nucleation) and increase the risk of decompression sickness (DCS). The timing, pattern and intensity of musculoskeletal activity are likely critical to the net effect. The NASA Prebreathe Reduction Program (PRP) combined oxygen prebreathe and exercise preceding a 4.3 psia exposure in non-ambulatory subjects (a microgravity analog) to produce two protocols now used by astronauts preparing for extravehicular activity - one employing cycling and non-cycling exercise (CEVIS: 'cycle ergometer vibration isolation system') and one relying on non-cycling exercise only (ISLE: 'in-suit light exercise'). Current efforts investigate whether light exercise normal to 1 G environments increases the risk of DCS over microgravity simulation.

Formate-induced inhibition of the water-oxidizing complex of photosystem II studied by EPR.

PubMed

Feyziev, Y M; Yoneda, D; Yoshii, T; Katsuta, N; Kawamori, A; Watanabe, Y

2000-04-04

The effects of various formate concentrations on both the donor and the acceptor sides in oxygen-evolving PS II membranes (BBY particles) were examined. EPR, oxygen evolution and variable chlorophyll fluorescence have been observed. It was found that formate inhibits the formation of the S(2) state multiline signal concomitant with stimulation of the Q(A)(-)Fe(2+) signal at g = 1.82. The decrease and the increase in intensities of the multiline and Q(A)(-)Fe(2+) signals, respectively, had a linear relation for formate concentrations between 5 and 500 mM. The g = 4.1 signal formation measured in the absence of methanol was not inhibited by formate up to 250 mM in the buffer. In the presence of 3% methanol the g = 4.1 signal evolved as formate concentration increased. The evolved signal could be ascribed to the inhibited centers. Oxygen evolution measured in the presence of an electron acceptor, phenyl-p-benzoquinone, was also inhibited by formate proportionally to the decrease in the multiline signal intensity. The inhibition seemed to be due to a retarded electron transfer from the water-oxidizing complex to Y(Z)(+), which was observed in the decay kinetics of the Y(Z)(+) signal induced by illumination above 250 K. These results show that formate induces inhibition of water oxidation reactions as well as electron transfer on the PS II acceptor side. The inhibition effects of formate in PS II were found to be reversible, indicating no destructive effect on the reaction center induced by formate.

Rapid oxygenation of Earth's atmosphere 2.33 billion years ago.

PubMed

Luo, Genming; Ono, Shuhei; Beukes, Nicolas J; Wang, David T; Xie, Shucheng; Summons, Roger E

2016-05-01

Molecular oxygen (O2) is, and has been, a primary driver of biological evolution and shapes the contemporary landscape of Earth's biogeochemical cycles. Although "whiffs" of oxygen have been documented in the Archean atmosphere, substantial O2 did not accumulate irreversibly until the Early Paleoproterozoic, during what has been termed the Great Oxygenation Event (GOE). The timing of the GOE and the rate at which this oxygenation took place have been poorly constrained until now. We report the transition (that is, from being mass-independent to becoming mass-dependent) in multiple sulfur isotope signals of diagenetic pyrite in a continuous sedimentary sequence in three coeval drill cores in the Transvaal Supergroup, South Africa. These data precisely constrain the GOE to 2.33 billion years ago. The new data suggest that the oxygenation occurred rapidly-within 1 to 10 million years-and was followed by a slower rise in the ocean sulfate inventory. Our data indicate that a climate perturbation predated the GOE, whereas the relationships among GOE, "Snowball Earth" glaciation, and biogeochemical cycling will require further stratigraphic correlation supported with precise chronologies and paleolatitude reconstructions.

Alcohol dehydrogenase and hydrogenase transcript fluctuations during a day-night cycle in Chlamydomonas reinhardtii: the role of anoxia.

PubMed

Whitney, Larisa Angela Swirsky; Loreti, Elena; Alpi, Amedeo; Perata, Pierdomenico

2011-04-01

• The unicellular green alga Chlamydomonas reinhardtii contains two iron (Fe)-hydrogenases which are responsible for hydrogen production under anoxia. In the present work the patterns of expression of alcohol dehydrogenase, a typical anaerobic gene in plants, of the hydrogenases genes (HYD1, HYD2) and of the genes responsible for their maturation (HYDEF, HYDG), were analysed. • The expression patterns were analysed by real-time reverse-transcription polymerase chain reaction in Chlamydomonas cultures during the day-night cycle, as well as in response to oxygen availability. • The results indicated that ADH1, HYD1, HYD2, HYDEF and HYDG were expressed following precise day-night fluctuations. ADH1 and HYD2 were modulated by the day-night cycle. Low oxygen plays an important role for the induction of HYD1, HYDEF and HYDG, while ADH1 and HYD2 expression was relatively insensitive to oxygen availability. • The regulation of the anaerobic gene expression in Chlamydomonas is only partly explained by responses to anoxia. The cell cycle and light-dark cycles are equally important elements in the regulatory network modulating the anaerobic response in Chlamydomonas. © The Authors (2010). Journal compilation © New Phytologist Trust (2010).

Antioxidant Activity of Oxygen Evolving Enhancer Protein 1 Purified from Capsosiphon fulvescens.

PubMed

Kim, Eun-Young; Choi, Youn Hee; Lee, Jung Im; Kim, In-Hye; Nam, Taek-Jeong

2015-06-01

This study was conducted to determine the antioxidant activity of a protein purified from Capsosiphon fulvescens. The purification steps included sodium acetate (pH 6) extraction and diethylaminoethyl-cellulose, reversed phase Shodex C4P-50 column chromatography. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis indicated that the molecular weight of the purified protein was 33 kDa. The N-terminus and partial peptide amino acid sequence of this protein was identical to the sequence of oxygen evolving enhancer (OEE) 1 protein. The antioxidant activity of the OEE 1 was determined in vitro using a scavenging test with 4 types of reactive oxygen species (ROS), including the 2,2-diphenyl-1-picrylhydrazyl radical, hydroxyl radical, superoxide anion, and hydrogen peroxide (H2 O2 ). OEE 1 had higher H2 O2 scavenging activity, which proved to be the result of enzymatic antioxidants rather than nonenzymatic antioxidants. In addition, OEE 1 showed less H2 O2 -mediated ROS formation in HepG2 cells. In conclusion, this study demonstrates that OEE 1 purified from C. fulvescens is an excellent antioxidant. © 2015 Institute of Food Technologists®

In vivo system for analyzing the function of the PsbP protein using Chlamydomonas reinhardtii.

PubMed

Nishimura, Taishi; Sato, Fumihiko; Ifuku, Kentaro

2017-09-01

The PsbP protein is an extrinsic subunit of photosystem II (PSII) specifically developed in green-plant species including land plants and green algae. The protein-protein interactions involving PsbP and its effect on oxygen evolution have been investigated in vitro using isolated PSII membranes. However, the importance of those interactions needs to be examined at the cellular level. To this end, we developed a system expressing exogenous PsbP in the background of the Chlamydomonas BF25 mutant lacking native PsbP. Expression of His-tagged PsbP successfully restored the oxygen-evolving activity and photoautotrophic growth of the mutant, while PsbP-∆15 lacking the N-terminal 15 residues, which are crucial for the oxygen-evolving activity of spinach PSII in vitro, only partially did. This demonstrated the importance of N-terminal sequence of PsbP for the photosynthetic activity in vivo. Furthermore, the PSII-LHCII supercomplex can be specifically purified from the Chlamydomonas cells having His-tagged PsbP using a metal affinity chromatography. This study provides a platform not only for the functional analysis of PsbP in vivo but also for structural analysis of the PSII-LHCII supercomplex from green algae.

Chemical Equilibrium Models for the S3 State of the Oxygen-Evolving Complex of Photosystem II.

PubMed

Isobe, Hiroshi; Shoji, Mitsuo; Shen, Jian-Ren; Yamaguchi, Kizashi

2016-01-19

We have performed hybrid density functional theory (DFT) calculations to investigate how chemical equilibria can be described in the S3 state of the oxygen-evolving complex in photosystem II. For a chosen 340-atom model, 1 stable and 11 metastable intermediates have been identified within the range of 13 kcal mol(-1) that differ in protonation, charge, spin, and conformational states. The results imply that reversible interconversion of these intermediates gives rise to dynamic equilibria that involve processes with relocations of protons and electrons residing in the Mn4CaO5 cluster, as well as bound water ligands, with concomitant large changes in the cluster geometry. Such proton tautomerism and redox isomerism are responsible for reversible activation/deactivation processes of substrate oxygen species, through which Mn-O and O-O bonds are transiently ruptured and formed. These results may allow for a tentative interpretation of kinetic data on substrate water exchange on the order of seconds at room temperature, as measured by time-resolved mass spectrometry. The reliability of the hybrid DFT method for the multielectron redox reaction in such an intricate system is also addressed.

Alteration of the α1β2/α2β1 subunit interface contributes to the increased hemoglobin-oxygen affinity of high-altitude deer mice

PubMed Central

Inoguchi, Noriko; Mizuno, Nobuhiro; Baba, Seiki; Kumasaka, Takashi; Natarajan, Chandrasekhar; Storz, Jay F.

2017-01-01

Background Deer mice (Peromyscus maniculatus) that are native to high altitudes in the Rocky Mountains have evolved hemoglobins with an increased oxygen-binding affinity relative to those of lowland conspecifics. To elucidate the molecular mechanisms responsible for the evolved increase in hemoglobin-oxygen affinity, the crystal structure of the highland hemoglobin variant was solved and compared with the previously reported structure for the lowland variant. Results Highland hemoglobin yielded at least two crystal types, in which the longest axes were 507 and 230 Å. Using the smaller unit cell crystal, the structure was solved at 2.2 Å resolution. The asymmetric unit contained two tetrameric hemoglobin molecules. Conclusions The analyses revealed that αPro50 in the highland hemoglobin variant promoted a stable interaction between αHis45 and heme that was not seen in the αHis50 lowland variant. The αPro50 mutation also altered the nature of atomic contacts at the α1β2/α2β1 intersubunit interfaces. These results demonstrate how affinity-altering changes in intersubunit interactions can be produced by mutations at structurally remote sites. PMID:28362841

[(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

PubMed Central

Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

2010-01-01

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

Alteration of the α1β2/α2β1 subunit interface contributes to the increased hemoglobin-oxygen affinity of high-altitude deer mice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inoguchi, Noriko; Mizuno, Nobuhiro; Baba, Seiki

2017-03-31

Deer mice (Peromyscus maniculatus) that are native to high altitudes in the Rocky Mountains have evolved hemoglobins with an increased oxygen-binding affinity relative to those of lowland conspecifics. To elucidate the molecular mechanisms responsible for the evolved increase in hemoglobin-oxygen affinity, the crystal structure of the highland hemoglobin variant was solved and compared with the previously reported structure for the lowland variant. Highland hemoglobin yielded at least two crystal types, in which the longest axes were 507 and 230 Å. Using the smaller unit cell crystal, the structure was solved at 2.2 Å resolution. The asymmetric unit contained two tetramericmore » hemoglobin molecules. The analyses revealed that αPro50 in the highland hemoglobin variant promoted a stable interaction between αHis45 and heme that was not seen in the αHis50 lowland variant. The αPro50 mutation also altered the nature of atomic contacts at the α1β2/α2β1 intersubunit interfaces. These results demonstrate how affinity-altering changes in intersubunit interactions can be produced by mutations at structurally remote sites.« less

Research on rechargeable oxygen electrodes.

NASA Technical Reports Server (NTRS)

Giner, J.; Holleck, G.; Malachesky, P. A.

1970-01-01

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Pressure gradient passivation of carbonaceous material normally susceptible to spontaneous combustion

DOEpatents

Ochs, Thomas L.; Sands, William D.; Schroeder, Karl; Summers, Cathy A.; Utz, Bruce R.

2002-01-29

This invention is a process for the passivation or deactivation with respect to oxygen of a carbonaceous material by the exposure of the carbonaceous material to an oxygenated gas in which the oxygenated gas pressure is increased from a first pressure to a second pressure and then the pressure is changed to a third pressure. Preferably a cyclic process which comprises exposing the carbonaceous material to the gas at low pressure and increasing the pressure to a second higher pressure and then returning the pressure to a lower pressure is used. The cycle is repeated at least twice wherein the higher pressure may be increased after a selected number of cycles.

Pressure gradient passivation of carbonaceous material normally susceptible to spontaneous combustion

DOEpatents

Ochs, Thomas L.; Sands, William D.; Schroeder, Karl; Summers, Cathy A.; Utz, Bruce R.

2000-11-14

This invention is a process for the passivation or deactivation with resp to oxygen of a carbonaceous material by the exposure of the carbonaceous material to an oxygenated gas in which the oxygenated gas pressure is increased from a first pressure to a second pressure and then the pressure is changed to a third pressure. Preferably a cyclic process which comprises exposing the carbonaceous material to the gas at low pressure and increasing the pressure to a second higher pressure and then returning the pressure to a lower pressure is used. The cycle is repeated at least twice wherein the higher pressure may be increased after a selected number of cycles.

Space station propulsion technology

NASA Technical Reports Server (NTRS)

Briley, G. L.

1986-01-01

The progress on the Space Station Propulsion Technology Program is described. The objectives are to provide a demonstration of hydrogen/oxygen propulsion technology readiness for the Initial Operating Capability (IOC) space station application, specifically gaseous hydrogen/oxygen and warm hydrogen thruster concepts, and to establish a means for evolving from the IOC space station propulsion to that required to support and interface with advanced station functions. The evaluation of concepts was completed. The accumulator module of the test bed was completed and, with the microprocessor controller, delivered to NASA-MSFC. An oxygen/hydrogen thruster was modified for use with the test bed and successfully tested at mixture ratios from 4:1 to 8:1.

Lipid oxidation in minced beef meat with added Krebs cycle substrates to stabilise colour.

PubMed

Yi, G; Grabež, V; Bjelanovic, M; Slinde, E; Olsen, K; Langsrud, O; Phung, V T; Haug, A; Oostindjer, M; Egelandsdal, B

2015-11-15

Krebs cycle substrates (KCS) can stabilise the colour of packaged meat by oxygen reduction. This study tested whether this reduction releases reactive oxygen species that may lead to lipid oxidation in minced meat under two different storage conditions. KCS combinations of succinate and glutamate increased peroxide forming potential (PFP, 1.18-1.32 mmol peroxides/kg mince) and thiobarbituric acid reactive substances (TBARS, 0.30-0.38 mg malondialdehyde (MDA) equivalents/kg mince) under low oxygen storage conditions. Both succinate and glutamate were metabolised. Moreover, under high oxygen (75%) storage conditions, KCS combinations of glutamate, citrate and malate increased PFP (from 1.22 to 1.29 mmol peroxides/kg) and TBARS (from 0.37 to 0.40 mg MDA equivalents/kg mince). Only glutamate was metabolised. The KCS combinations that were added to stabilise colour were metabolised during storage, and acted as pro-oxidants that promoted lipid oxidation in both high and low oxygen conditions. Copyright © 2015. Published by Elsevier Ltd.

The effect of dietary nitrate supplementation on the oxygen cost of cycling, walking performance and resting blood pressure in individuals with chronic obstructive pulmonary disease: A double blind placebo controlled, randomised control trial.

PubMed

Shepherd, Anthony I; Wilkerson, Daryl P; Dobson, Lee; Kelly, James; Winyard, Paul G; Jones, Andrew M; Benjamin, Nigel; Shore, Angela C; Gilchrist, Mark

2015-08-01

Chronic obstructive pulmonary disease (COPD) results in exercise intolerance. Dietary nitrate supplementation has been shown to lower blood pressure (BP), reduce the oxygen cost of exercise, and enhance exercise tolerance in healthy volunteers. This study assessed the effects of dietary nitrate on the oxygen cost of cycling, walking performance and BP in individuals with mild-moderate COPD. Thirteen patients with mild-moderate COPD were recruited. Participants consumed 70 ml of either nitrate-rich (6.77 mmol nitrate; beetroot juice) or nitrate-depleted beetroot juice (0.002 mmol nitrate; placebo) twice a day for 2.5 days, with the final supplement ~3 hours before testing. BP was measured before completing two bouts of moderate-intensity cycling, where pulmonary gas exchange was measured throughout. The six-minute walk test (6 MWT) was completed 30 minutes subsequent to the second cycling bout. Plasma nitrate concentration was significantly elevated following beetroot juice vs. placebo (placebo; 48 ± 86 vs. beetroot juice; 215 ± 84 µM, P = 0.002). No significant differences were observed between placebo vs. beetroot juice for oxygen cost of exercise (933 ± 323 vs. 939 ± 302 ml: min(-1); P = 0.88), distance covered in the 6 MWT (456 ± 86 vs. 449 ± 79 m; P = 0.37), systolic BP (123 ± 14 vs. 123 ± 14 mmHg; P = 0.91), or diastolic BP (77 ± 9 vs. 79 ± 9 mmHg; P = 0.27). Despite a large rise in plasma nitrate concentration, two days of nitrate supplementation did not reduce the oxygen cost of moderate intensity cycling, increase distance covered in the 6 MWT, or lower BP. Copyright © 2015 Elsevier Inc. All rights reserved.

Fumarate Reductase Activity Maintains an Energized Membrane in Anaerobic Mycobacterium tuberculosis

PubMed Central

Watanabe, Shinya; Zimmermann, Michael; Goodwin, Michael B.; Sauer, Uwe; Barry, Clifton E.; Boshoff, Helena I.

2011-01-01

Oxygen depletion of Mycobacterium tuberculosis engages the DosR regulon that coordinates an overall down-regulation of metabolism while up-regulating specific genes involved in respiration and central metabolism. We have developed a chemostat model of M. tuberculosis where growth rate was a function of dissolved oxygen concentration to analyze metabolic adaptation to hypoxia. A drop in dissolved oxygen concentration from 50 mmHg to 0.42 mmHg led to a 2.3 fold decrease in intracellular ATP levels with an almost 70-fold increase in the ratio of NADH/NAD+. This suggests that re-oxidation of this co-factor becomes limiting in the absence of a terminal electron acceptor. Upon oxygen limitation genes involved in the reverse TCA cycle were upregulated and this upregulation was associated with a significant accumulation of succinate in the extracellular milieu. We confirmed that this succinate was produced by a reversal of the TCA cycle towards the non-oxidative direction with net CO2 incorporation by analysis of the isotopomers of secreted succinate after feeding stable isotope (13C) labeled precursors. This showed that the resulting succinate retained both carbons lost during oxidative operation of the TCA cycle. Metabolomic analyses of all glycolytic and TCA cycle intermediates from 13C-glucose fed cells under aerobic and anaerobic conditions showed a clear reversal of isotope labeling patterns accompanying the switch from normoxic to anoxic conditions. M. tuberculosis encodes three potential succinate-producing enzymes including a canonical fumarate reductase which was highly upregulated under hypoxia. Knockout of frd, however, failed to reduce succinate accumulation and gene expression studies revealed a compensatory upregulation of two homologous enzymes. These major realignments of central metabolism are consistent with a model of oxygen-induced stasis in which an energized membrane is maintained by coupling the reductive branch of the TCA cycle to succinate secretion. This fermentative process may offer unique targets for the treatment of latent tuberculosis. PMID:21998585

Fire feedbacks over geological time and the evolution of atmospheric oxygen concentration

NASA Astrophysics Data System (ADS)

Mills, B.; Belcher, C.; Lenton, T. M.

2017-12-01

During the 4.5 billion year history of the Earth, the concentration of oxygen in the atmosphere has risen from trace levels to today's 21%. Yet over the last 400 million years, O2 concentration appears to have remained within a relatively narrow range (around 15% - 30%), despite dramatic changes in the nature of global biogeochemical cycling. This stability has been crucial for continued animal evolution, and is thought to have arisen through feedbacks between oxygen, wildfire and plant productivity: the strong oxygen- dependence of fire initiation and spread means that global photosynthetic primary productivity is suppressed when oxygen levels are high, and enhanced when levels are low. We present biogeochemical modelling of the long term carbon and oxygen cycles, which aims to capture the operation of the wildfire feedback alongside other key processes. We find that wildfire can effectively stabilize long term oxygen concentrations, but that the nature of this feedback has changed as plant evolution has provided different fuels. Specifically, the evolution of early angiosperms during the Cretaceous period provided new understory fuels that more easily facilitated crown and canopy fires. Adding these dynamics to our model produces a more stable system over long timescales, and the model predicts that oxygen concentration has declined towards the present day - a prediction that is supported by other independent estimates.

The Role of Low-coordinate Oxygen on Co3O4(110) in Catalytic Oxidation of CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Deen; Dai, Sheng

2011-01-01

A complete catalytic cycle for carbon monoxide (CO) oxidation to carbon dioxide (CO{sub 2}) by molecular oxygen on the Co{sub 3}O{sub 4}(110) surface was obtained by density functional theory plus the on-site Coulomb repulsion (DFT + U). Previously observed high activity of Co{sub 3}O{sub 4} to catalytically oxidize CO at very low temperatures is explained by a unique twofold-coordinate oxygen site on Co{sub 3}O{sub 4}(110). The CO molecule extracts this oxygen with a computed barrier of 27 kJ/mol. The extraction leads to CO{sub 2} formation and an oxygen vacancy on Co{sub 3}O{sub 4}(110). Then, the O{sub 2} molecule dissociates withoutmore » a barrier between two neighboring oxygen vacancies (which are shown to have high surface mobility), thereby replenishing the twofold-coordinate oxygen sites on the surface and enabling the catalytic cycle. In contrast, extracting the threefold-coordinate oxygen site on Co{sub 3}O{sub 4}(110) has a higher barrier. Our work furnishes a molecular-level mechanism of Co{sub 3}O{sub 4}'s catalytic power, which may help understand previous experimental results and oxidation catalysis by transition metal oxides.« less

Simultaneous sampling of tissue oxygenation and oxygen consumption in skeletal muscle.

PubMed

Nugent, William H; Song, Bjorn K; Pittman, Roland N; Golub, Aleksander S

2016-05-01

Under physiologic conditions, microvascular oxygen delivery appears to be well matched to oxygen consumption in respiring tissues. We present a technique to measure interstitial oxygen tension (PISFO2) and oxygen consumption (VO2) under steady-state conditions, as well as during the transitions from rest to activity and back. Phosphorescence Quenching Microscopy (PQM) was employed with pneumatic compression cycling to achieve 1 to 10 Hz sampling rates of interstitial PO2 and simultaneous recurrent sampling of VO2 (3/min) in the exteriorized rat spinotrapezius muscle. The compression pressure was optimized to 120-130 mmHg without adverse effect on the tissue preparation. A cycle of 5s compression followed by 15s recovery yielded a resting VO2 of 0.98 ± 0.03 ml O2/100 cm(3)min while preserving microvascular oxygen delivery. The measurement system was then used to assess VO2 dependence on PISFO2 at rest and further tested under conditions of isometric muscle contraction to demonstrate a robust ability to monitor the on-kinetics of tissue respiration and the compensatory changes in PISFO2 during contraction and recovery. The temporal and spatial resolution of this approach is well suited to studies seeking to characterize microvascular oxygen supply and demand in thin tissues. Copyright © 2015 Elsevier Inc. All rights reserved.

Experimental evolution of an alternating uni- and multicellular life cycle in Chlamydomonas reinhardtii

PubMed Central

Ratcliff, William C.; Herron, Matthew D.; Howell, Kathryn; Pentz, Jennifer T.; Rosenzweig, Frank; Travisano, Michael

2013-01-01

The transition to multicellularity enabled the evolution of large, complex organisms, but early steps in this transition remain poorly understood. Here we show that multicellular complexity, including development from a single cell, can evolve rapidly in a unicellular organism that has never had a multicellular ancestor. We subject the alga Chlamydomonas reinhardtii to conditions that favour multicellularity, resulting in the evolution of a multicellular life cycle in which clusters reproduce via motile unicellular propagules. While a single-cell genetic bottleneck during ontogeny is widely regarded as an adaptation to limit among-cell conflict, its appearance very early in this transition suggests that it did not evolve for this purpose. Instead, we find that unicellular propagules are adaptive even in the absence of intercellular conflict, maximizing cluster-level fecundity. These results demonstrate that the unicellular bottleneck, a trait essential for evolving multicellular complexity, can arise rapidly via co-option of the ancestral unicellular form. PMID:24193369

Repositories for Research: Southampton's Evolving Role in the Knowledge Cycle

ERIC Educational Resources Information Center

Simpson, Pauline; Hey, Jessie

2006-01-01

Purpose: To provide an overview of how open access (OA) repositories have grown to take a premier place in the e-research knowledge cycle and offer Southampton's route from project to sustainable institutional repository. Design/methodology/approach: The evolution of institutional repositories and OA is outlined raising questions of multiplicity…

DHA-rich Fish Oil Increases the Omega-3 Index and Lowers the Oxygen Cost of Physiologically Stressful Cycling in Trained Individuals.

PubMed

Hingley, Lachlan; Macartney, Michael J; Brown, Marc A; McLennan, Peter L; Peoples, Gregory E

2017-08-01

Dietary fish oil, providing docosahexaenoic acid (DHA) modulates oxygen consumption and fatigue in animal models. However, in humans predominately supplemented with high eicosapentaenoic acid (EPA), there is no evidence of endurance performance enhancement. Therefore, this study examined if DHA-rich fish oil could improve repeated bouts of physiologically stressful cycling and a subsequent time trial in a state of fatigue. Twenty-six trained males took part in a double-blind study and were supplemented with either 2 × 1g/day soy oil, Control) or DHA-rich tuna fish oil (Nu-Mega) (FO) (560mg DHA / 140mg eicosapentaenoic acid (EPA), for 8 weeks. Maximal cycling power (3 × 6s), isometric quadriceps strength (MVC), Wingate cycling protocol (6 × 30s) and a 5min cycling time-trial were assessed at baseline and eight weeks. The Omega-3 Index was not different at baseline (Control: 4.2 ± 0.2; FO: 4.7 ± 0.2%) and increased in the FO group after eight weeks (Control: 3.9 ± 0.2; FO: 6.3 ± 0.3%, p < .01). There was no effect of DHA-rich fish oil on power output of maximal 6s cycle sprinting (Control: Pre 1100 ± 49 Post 1067 ± 51; FO: Pre 1070 ± 46 Post 1042 ± 46W), during 5min time trail (Control: Pre 267 ± 19 Post 278 ± 20; FO: Pre 253 ± 16 Post 265 ± 16 W) or maximal voluntary contraction force (Control: Pre 273 ± 19 Post 251 ± 19; FO: Pre 287 ± 17 Post 283 ± 16 Nm). Nevertheless, relative oxygen consumption was reduced the FO group during the cycling time trial (Control: -23 ± 26; FO: -154 ± 59ml O2/min/100W p < .05) suggesting improved economy of cycling. We conclude that DHA-rich fish oil, successful at elevating the Omega-3 Index, and reflective of skeletal muscle membrane incorporation, can modulate oxygen consumption during intense exercise.

Oxygen and SO2 Consumption Rates in White and Rosé Wines: Relationship with and Effects on Wine Chemical Composition.

PubMed

Carrascón, Vanesa; Bueno, Mónica; Fernandez-Zurbano, Purificación; Ferreira, Vicente

2017-11-01

This Article addresses the study of O 2 and SO 2 consumption rates of white and rosé wines, their relationship to the initial chemical composition, and their effects on the chemical changes experienced by wine during oxidation. Eight wines were subjected to five consecutive air-saturation cycles. O 2 was monitored periodically; SO 2 , color, and antioxidant indexes were determined after each cycle, and the initial and final compositions of the wines were thoroughly determined. Wines consumed oxygen at progressively decreasing rates. In the last cycles, after a strong decrease, consistent increases of oxygen levels were seen. Oxygen consumption rates were satisfactorily modeled, being proportional to wine copper, quercetin, and kaempherol contents and negatively proportional to cinnamic acids. SO 2 consumption rates were highly diverse between wines and were positively related to free SO 2 , Mn, and pH, among others. In the last saturations, SO 2 consumption took place regardless of O 2 consumption, implying that SO 2 should reduce chemical species oxidized in previous saturations. Some volatile phenols seem to be the end point of radical-mediated oxidation of polyphenols taking place preferably in the first saturation.

Optimization of Intermittent Hyperbaric Oxygen Exposures by Duration of Oxygen Cycles

DTIC Science & Technology

2012-01-01

IL-1β, IL-6 as a marker of HBO2 toxicity; and (2) by gene expression of heat shock protein 70 (HSP70) as a potential protective factor against... potential use in clinical and military exposures and dives. For this reason, alternation of 30 and 60 min HBO2 cycles with 10 min hyperbaric air breaks was... potential fire/explosion hazards of exposure to several atmospheres of 100% O2. In addition, environmental factors, such as CO2 buildup

B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Shidong; Xu, Wu; Cao, Ruiguo

Lithium-oxygen (Li-O 2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B 4C) as the non-carbon based oxygen electrode material for aprotic Li-O 2 batteries. B 4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable formore » battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O 2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B 4C based electrode is mainly due to be the loss of active sites on B 4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B 4C is a very promising alternative oxygen electrode material for aprotic Li-O 2 batteries. It can also be used as a standard electrode to investigate the stability of electrolytes.« less

Partitioning the Fitness Components of RNA Populations Evolving In Vitro

PubMed Central

Díaz Arenas, Carolina; Lehman, Niles

2013-01-01

All individuals in an evolving population compete for resources, and their performance is measured by a fitness metric. The performance of the individuals is relative to their abilities and to the biotic surroundings – the conditions under which they are competing – and involves many components. Molecules evolving in a test tube can also face complex environments and dynamics, and their fitness measurements should reflect the complexity of various contributing factors as well. Here, the fitnesses of a set of ligase ribozymes evolved by the continuous in vitro evolution system were measured. During these evolution cycles there are three different catalytic steps, ligation, reverse transcription, and forward transcription, each with a potential differential influence on the total fitness of each ligase. For six distinct ligase ribozyme genotypes that resulted from continuous evolution experiments, the rates of reaction were measured for each catalytic step by tracking the kinetics of enzymes reacting with their substrates. The reaction products were analyzed for the amount of product formed per time. Each catalytic step of the evolution cycle was found to have a differential incidence in the total fitness of the ligases, and therefore the total fitness of any ligase cannot be inferred from only one catalytic step of the evolution cycle. Generally, the ribozyme-directed ligation step tends to impart the largest effect on overall fitness. Yet it was found that the ligase genotypes have different absolute fitness values, and that they exploit different stages of the overall cycle to gain a net advantage. This is a new example of molecular niche partitioning that may allow for coexistence of more than one species in a population. The dissection of molecular events into multiple components of fitness provides new insights into molecular evolutionary studies in the laboratory, and has the potential to explain heretofore counterintuitive findings. PMID:24391957

Electrolytic production of metals using a resistant anode

DOEpatents

Tarcy, Gary P.; Gavasto, Thomas M.; Ray, Siba P.

1986-01-01

An electrolytic process comprising evolving oxygen on an anode in a molten salt, the anode comprising an alloy comprising a first metal and a second metal, both metals forming oxides, the oxide of the first metal being more resistant than the second metal to attack by the molten salt, the oxide of the second metal being more resistant than the first metal to the diffusion of oxygen. The electrode may also be formed of CuAlO.sub.2 and/or Cu.sub.2 O.

Effect of cycling on the lithium/electrolyte interface in organic electrolytes

NASA Technical Reports Server (NTRS)

Surampudi, S.; Shen, D. H.; Huang, C.-K.; Narayanan, S. R.; Attia, A.; Halpert, G.; Peled, E.

1993-01-01

Nondestructive methods such as ac impedance spectroscopy and microcalorimetry are used to study the effect of cell cycling on the lithium/electrolyte interface. The reactivity of both uncycled and cycled lithium towards various electrolytes is examined by measuring the heat evolved from the cells under open-circuit conditions at 25 C by microcalorimetry. Cycled cells at the end of charge/discharge exhibited considerably higher heat output compared with the uncycled cells. After 30 d of storage, the heat output of the cycled cells is similar to that of the uncycled cells. The cell internal resistance increases with cycling, and this is attributed to the degradation of the electrolyte with cycling.

Reliability of Near-Infrared Spectroscopy for Determining Muscle Oxygen Saturation during Exercise

ERIC Educational Resources Information Center

Austin, Krista G.; Daigle, Karen A.; Patterson, Patricia; Cowman, Jason; Chelland, Sara; Haymes, Emily M.

2005-01-01

Near-infrared spectroscopy is currently used to assess changes in the oxygen saturation of the muscle during exercise. The primary purpose of this study was to assess the reliability of near-infrared spectroscopy in determining muscle oxygen saturation (StO[subscript 2]) in the vastus lateralis during cycling and the gastrocnemius during running…

Cyclic fatigue analysis of rocket thrust chambers. Volume 1: OFHC copper chamber low cycle fatigue

NASA Technical Reports Server (NTRS)

Miller, R. W.

1974-01-01

A three-dimensional finite element elasto-plastic strain analysis was performed for the throat section of a regeneratively cooled rocket combustion chamber. The analysis employed the RETSCP finite element computer program. The analysis included thermal and pressure loads, and the effects of temperature dependent material properties, to determine the strain range corresponding to the chamber operating cycle. The analysis was performed for chamber configuration and operating conditions corresponding to a hydrogen-oxygen combustion chamber which was fatigue tested to failure. The computed strain range at typical chamber operating conditions was used in conjunction with oxygen-free, high-conductivity (OHFC) copper isothermal fatigue test data to predict chamber low-cycle fatigue life.

Regenerative Fuel Cell Test Rig Completed and Operational at Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.

2004-01-01

The NASA Glenn Research Center has completed construction of its first closed-cycle hydrogen-oxygen regenerative fuel cell (RFC). The RFC is an electrochemical system that collects and stores solar energy during the day then releases that energy at night, thus making the Sun's energy available all 24 hours. It consists of a dedicated hydrogen-oxygen fuel cell stack and an electrolyzer stack, the interconnecting plumbing and valves, cooling pumps, water transfer pumps, gas recirculation pumps, phase separators, storage tanks for oxygen (O2) and hydrogen (H2), heat exchangers, isolation valves, pressure regulators, nitrogen purge provisions, instrumentation, and other components. It includes all the equipment required to (1) absorb electrical power from an outside source and store it as pressurized hydrogen and oxygen and (2) make electrical power from the stored gases, saving the product water for reuse during the next cycle.

Reactive Oxygen Species in Cardiovascular Disease

PubMed Central

Sugamura, Koichi; Keaney, John F.

2011-01-01

Based on the ‘free-radical theory’ of disease, researchers have been trying to elucidate the role of oxidative stress from free radicals in cardiovascular disease. Considerable data indicate that ROS and oxidative stress are important features of cardiovascular diseases including atherosclerosis, hypertension, and congestive heart failure. However, blanket strategies with antioxidants to ameliorate cardiovascular disease have not generally yielded favorable results. However, our understanding or reactive oxygen species has evolved to the point that we now realize these species have important roles in physiology as well as pathophysiology. Thus, it is overly simplistic to assume a general antioxidant strategy will yield specific effects on cardiovascular disease. Indeed, there are several sources of reactive oxygen species that are known to be active in the cardiovascular system. This review will address our understanding of reactive oxygen species sources in cardiovascular disease and both animal and human data defining how reactive oxygen species contribute to physiology and pathology. PMID:21627987

Advancing Ocean Science Through Coordination, Community Building, and Outreach

NASA Astrophysics Data System (ADS)

Benway, H. M.

2016-02-01

The US Ocean Carbon and Biogeochemistry (OCB) Program (www.us-ocb.org) is a dynamic network of scientists working across disciplines to understand the ocean's role in the global carbon cycle and how marine ecosystems and biogeochemical cycles are responding to environmental change. The OCB Project Office, which is based at the Woods Hole Oceanographic Institution (WHOI), serves as a central information hub for this network, bringing different scientific disciplines together and cultivating partnerships with complementary US and international programs to address high-priority research questions. The OCB Project Office plays multiple important support roles, such as hosting and co-sponsoring workshops, short courses, working groups, and synthesis activities on emerging research issues; engaging with relevant national and international science planning initiatives; and developing education and outreach activities and products with the goal of promoting ocean carbon science to broader audiences. Current scientific focus areas of OCB include ocean observations (shipboard, autonomous, satellite, etc.); changing ocean chemistry (acidification, expanding low-oxygen conditions, etc.); ocean carbon uptake and storage; estuarine and coastal carbon cycling; biological pump and associated biological and biogeochemical processes and carbon fluxes; and marine ecosystem response to environmental and evolutionary changes, including physiological and molecular-level responses of individual organisms, as well as shifts in community structure and function. OCB is a bottom-up organization that responds to the continually evolving priorities and needs of its network and engages marine scientists at all career stages. The scientific leadership of OCB includes a scientific steering committee and subcommittees on ocean time-series, ocean acidification, and ocean fertilization. This presentation will highlight recent OCB activities and products of interest to the ocean science community.

Single-cell genomics reveals co-metabolic interactions within uncultivated Marine Group A bacteria

NASA Astrophysics Data System (ADS)

Hawley, A. K.; Hallam, S. J.

2016-02-01

Marine Group A (MGA) bacteria represent a ubiquitous and abundant candidate phylum enriched in oxygen minimum zones (OMZs) and the deep ocean. Despite MGA prevalence little is known about their ecology and biogeochemistry. Here we chart the metabolic potential of 26 MGA single-cell amplified genomes sourced from different environments spanning ecothermodynamic gradients including open ocean waters, OMZs and methanogenic environments including a terephthalate-degrading bioreactor. Metagenomic contig recruitment to SAGs combined with tetra-nucleotide frequency distribution patterns resolved nine MGA population genome bins. All population genomes exhibited genomic streamlining with open ocean MGA being the most reduced. Different strategies for carbohydrate utilization, carbon fixation energy metabolism and respiratory pathways were identified between population genome bins, including various roles in the nitrogen and sulfur cycles. MGA inhabiting OMZ oxyclines encoded genes for partial denitrification with potential to feed into anammox and nitrification as well as a polysulfide reductase with a potential role in the cryptic sulfur cycle. MGA inhabiting anoxic waters, encoded NiFe hydrogenase and nitrous oxide reductase with the potential to complete partial denitrification pathways previously linked to sulfur oxidation in SUP05 bacteria. MGA from methanogenic environments encoded genes mediating cascading syntrophic interactions with fatty acid degraders and methanogens including reverse electron transport potential. The MGA phylum appears to have evolved alternative metabolic innovations adapting specific subgroups to occupy specific niches along ecothermodynamic gradients. Additionally, expression of MGA genes from different OMZ environments supports that these subgroups manifest an increasing propensity for co-metabolic interactions under energy limiting conditions that mandates a cooperative mode of existence with important implications for C, N and S cycling in marine ecosystems.

Discontinuous gas-exchange cycle characteristics are differentially affected by hydration state and energy metabolism in gregarious and solitary desert locusts.

PubMed

Talal, Stav; Ayali, Amir; Gefen, Eran

2015-12-01

The termination of discontinuous gas exchange cycles (DGCs) in severely dehydrated insects casts doubt on the generality of the hygric hypothesis, which posits that DGCs evolved as a water conservation mechanism. We followed DGC characteristics in the two density-dependent phases of the desert locust Schistocerca gregaria throughout exposure to an experimental treatment of combined dehydration and starvation stress, and subsequent rehydration. We hypothesized that, under stressful conditions, the more stress-resistant gregarious locusts would maintain DGCs longer than solitary locusts. However, we found no phase-specific variations in body water content, water loss rates (total and respiratory) or timing of stress-induced abolishment of DGCs. Likewise, locusts of both phases re-employed DGCs after ingesting comparable volumes of water when rehydrated. Despite comparable water management performances, the effect of exposure to stressful experimental conditions on DGC characteristics varied significantly between gregarious and solitary locusts. Interburst duration, which is affected by the ability to buffer CO2, was significantly reduced in dehydrated solitary locusts compared with gregarious locusts. Moreover, despite similar rehydration levels, only gregarious locusts recovered their initial CO2 accumulation capacity, indicating that cycle characteristics are affected by factors other than haemolymph volume. Haemolymph protein measurements and calculated respiratory exchange ratios suggest that catabolism of haemolymph proteins may contribute to a reduced haemolymph buffering capacity, and thus a compromised ability for CO2 accumulation, in solitary locusts. Nevertheless, DGC was lost at similar hydration states in the two phases, suggesting that DGCs are terminated as a result of inadequate oxygen supply to the tissues. © 2015. Published by The Company of Biologists Ltd.

Genetic alterations in Krebs cycle and its impact on cancer pathogenesis.

PubMed

Sajnani, Karishma; Islam, Farhadul; Smith, Robert Anthony; Gopalan, Vinod; Lam, Alfred King-Yin

2017-04-01

Cancer cells exhibit alterations in many cellular processes, including oxygen sensing and energy metabolism. Glycolysis in non-oxygen condition is the main energy production process in cancer rather than mitochondrial respiration as in benign cells. Genetic and epigenetic alterations of Krebs cycle enzymes favour the shift of cancer cells from oxidative phosphorylation to anaerobic glycolysis. Mutations in genes encoding aconitase, isocitrate dehydrogenase, succinate dehydrogenase, fumarate hydratase, and citrate synthase are noted in many cancers. Abnormalities of Krebs cycle enzymes cause ectopic production of Krebs cycle intermediates (oncometabolites) such as 2-hydroxyglutarate, and citrate. These oncometabolites stabilize hypoxia inducible factor 1 (HIF1), nuclear factor like 2 (Nrf2), inhibit p53 and prolyl hydroxylase 3 (PDH3) activities as well as regulate DNA/histone methylation, which in turn activate cell growth signalling. They also stimulate increased glutaminolysis, glycolysis and production of reactive oxygen species (ROS). Additionally, genetic alterations in Krebs cycle enzymes are involved with increased fatty acid β-oxidations and epithelial mesenchymal transition (EMT) induction. These altered phenomena in cancer could in turn promote carcinogenesis by stimulating cell proliferation and survival. Overall, epigenetic and genetic changes of Krebs cycle enzymes lead to the production of oncometabolite intermediates, which are important driving forces of cancer pathogenesis and progression. Understanding and applying the knowledge of these mechanisms opens new therapeutic options for patients with cancer. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

The mechanism of enhanced wastewater nitrogen removal by photo-sequencing batch reactors based on comprehensive analysis of system dynamics within a cycle.

PubMed

Ye, Jianfeng; Liang, Junyu; Wang, Liang; Markou, Giorgos

2018-07-01

To understand the mechanism of enhanced nitrogen removal by photo-sequencing batch reactors (photo-SBRs), which incorporated microalgal photosynthetic oxygenation into the aerobic phases of a conventional cycle, this study performed comprehensive analysis of one-cycle dynamics. Under a low aeration intensity (about 0.02 vvm), a photo-SBR, illuminated with light at 92.27 μ·mol·m -2 ·s -1 , could remove 99.45% COD, 99.93% NH 4 + -N, 90.39% TN, and 95.17% TP, while the control SBR could only remove 98.36% COD, 83.51% NH 4 + -N, 78.96% TN, and 97.75% TP, for a synthetic domestic sewage. The specific oxygen production rate (SOPR) of microalgae in the photo-SBR could reach 6.63 fmol O 2 ·cell -1 ·h -1 . One-cycle dynamics shows that the enhanced nitrogen removal by photo-SBRs is related to photosynthetic oxygenation, resulting in strengthened nitrification, instead of direct nutrient uptake by microalgae. A too high light or aeration intensity could deteriorate anoxic conditions and thus adversely affect the removal of TN and TP in photo-SBRs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

PubMed

Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

2011-12-23

Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

NASA Technical Reports Server (NTRS)

Macdonald, D. D.; Pound, B. G.; Lenhart, S. J.

1989-01-01

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

Oxygen concentration inside a functioning photosynthetic cell.

PubMed

Kihara, Shigeharu; Hartzler, Daniel A; Savikhin, Sergei

2014-05-06

The excess oxygen concentration in the photosynthetic membranes of functioning oxygenic photosynthetic cells was estimated using classical diffusion theory combined with experimental data on oxygen production rates of cyanobacterial cells. The excess oxygen concentration within the plesiomorphic cyanobacterium Gloeobactor violaceus is only 0.025 μM, or four orders of magnitude lower than the oxygen concentration in air-saturated water. Such a low concentration suggests that the first oxygenic photosynthetic bacteria in solitary form could have evolved ∼2.8 billion years ago without special mechanisms to protect them against reactive oxygen species. These mechanisms instead could have been developed during the following ∼500 million years while the oxygen level in the Earth's atmosphere was slowly rising. Excess oxygen concentrations within individual cells of the apomorphic cyanobacteria Synechocystis and Synechococcus are 0.064 and 0.25 μM, respectively. These numbers suggest that intramembrane and intracellular proteins in isolated oxygenic photosynthetic cells are not subjected to excessively high oxygen levels. The situation is different for closely packed colonies of photosynthetic cells. Calculations show that the excess concentration within colonies that are ∼40 μm or larger in diameter can be comparable to the oxygen concentration in air-saturated water, suggesting that species forming colonies require protection against reactive oxygen species even in the absence of oxygen in the surrounding atmosphere. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Oxygen Concentration Inside a Functioning Photosynthetic Cell

PubMed Central

Kihara, Shigeharu; Hartzler, Daniel A.; Savikhin, Sergei

2014-01-01

The excess oxygen concentration in the photosynthetic membranes of functioning oxygenic photosynthetic cells was estimated using classical diffusion theory combined with experimental data on oxygen production rates of cyanobacterial cells. The excess oxygen concentration within the plesiomorphic cyanobacterium Gloeobactor violaceus is only 0.025 μM, or four orders of magnitude lower than the oxygen concentration in air-saturated water. Such a low concentration suggests that the first oxygenic photosynthetic bacteria in solitary form could have evolved ∼2.8 billion years ago without special mechanisms to protect them against reactive oxygen species. These mechanisms instead could have been developed during the following ∼500 million years while the oxygen level in the Earth’s atmosphere was slowly rising. Excess oxygen concentrations within individual cells of the apomorphic cyanobacteria Synechocystis and Synechococcus are 0.064 and 0.25 μM, respectively. These numbers suggest that intramembrane and intracellular proteins in isolated oxygenic photosynthetic cells are not subjected to excessively high oxygen levels. The situation is different for closely packed colonies of photosynthetic cells. Calculations show that the excess concentration within colonies that are ∼40 μm or larger in diameter can be comparable to the oxygen concentration in air-saturated water, suggesting that species forming colonies require protection against reactive oxygen species even in the absence of oxygen in the surrounding atmosphere. PMID:24806920

Modeling the Oxygen Cycle in the Equatorial Pacific: Regulation of Physical and Biogeochemical Processes

NASA Astrophysics Data System (ADS)

Wang, X.; Murtugudde, R. G.; Zhang, D.

2016-12-01

Photosynthesis and respiration are important processes in all ecosystems on the Earth, in which carbon and oxygen are the two main elements. However, the oxygen cycle has received much less attention (relative to the carbon cycle) despite its big role in the earth system. Oxygen is a sensitive indicator of physical and biogeochemical processes in the ocean thus a key parameter for understanding the ocean's ecosystem and biogeochemistry. The Oxygen-Minimum-Zone (OMZ), often seen below 200 m, is a profound feature in the world oceans. There has been evidence of OMZ expansion over the past few decades in the tropical oceans. Climate models project that there would be a continued decline in dissolved oxygen (DO) and an expansion of the tropical OMZs under future warming conditions, which is of great concern because of the implications for marine organisms. We employ a validated three-dimensional model that simulates physical transport (circulation and vertical mixing), biological processes (O2 production and consumption) and ocean-atmosphere O2 exchange to quantify various sources and sinks of DO over 1980-2015. We show how we use observational data to improve our model simulation. Then we assess the spatial and temporal variability in simulated DO in the tropical Pacific Ocean, and explore the impacts of physical and biogeochemical processes on the DO dynamics, with a focus on the MOZ. Our analyses indicate that DO in the OMZ has a positive relationship with the 13ºC isotherm depth and a negative relationship with the concentration of dissolved organic material.

Dark chocolate supplementation reduces the oxygen cost of moderate intensity cycling.

PubMed

Patel, Rishikesh Kankesh; Brouner, James; Spendiff, Owen

2015-01-01

Dark chocolate (DC) is abundant in flavanols which have been reported to increase the bioavailability and bioactivity of nitric oxide (NO). Increasing NO bioavailability has often demonstrated reduced oxygen cost and performance enhancement during submaximal exercise. Nine moderately-trained male participants volunteered to undertake baseline (BL) measurements that comprised a cycle V̇O(2max) test followed by cycling at 80% of their established gas exchange threshold (GET) for 20-min and then immediately followed by a two-minute time-trial (TT). Using a randomised crossover design participants performed two further trials, two weeks apart, with either 40 g of DC or white chocolate (WC) being consumed daily. Oxygen consumption, RER, heart rate and blood lactate (BLa) were measured during each trial. DC consumption increased GET and TT performance compared to both BL and WC (P < 0.05). DC consumption increased V̇O(2max) by 6% compared to BL (P < 0.05), but did not reach statistical significance compared to WC. There were no differences in the moderate-intensity cycling for V̇O₂, RER, BLa and heart rate between conditions, although, V̇O₂ and RER exhibited consistently lower trends following DC consumption compared to BL and WC, these did not reach statistical significance. Chronic supplementation with DC resulted in a higher GET and enhanced TT performance. Consequently, ingestion of DC reduced the oxygen cost of moderate intensity exercise and may be an effective ergogenic aid for short-duration moderate intensity exercise.

Reproducing the Photospheric Magnetic Field Evolution during the Rise of Cycle 24 with Flux Transport by Supergranules

NASA Technical Reports Server (NTRS)

Hathaway, David; Upton, Lisa

2012-01-01

We simulate the transport of magnetic flux in the Sun s photosphere by an evolving pattern of cellular horizontal flows (supergranules). Characteristics of the simulated flow pattern can match observed characteristics including the velocity power spectrum, cell lifetimes, and cell motions in longitude and latitude. Simulations using an average, and north-south symmetric, meridional motion of the cellular pattern produce polar magnetic fields that are too weak in the North and too strong in the South. Simulations using cellular patterns with meridional motions that evolve with the observed changes in strength and north-south asymmetry will be analyzed to see if they reproduce the polar field evolution observed during the rise of Cycle 24.

Reproducing the Photospheric Magnetic Field Evolution During the Rise of Cycle 24 with Flux Transport by Supergranules

NASA Technical Reports Server (NTRS)

Hathaway, David H.; Upton, Lisa

2012-01-01

We simulate the transport of magnetic flux in the Sun s photosphere by an evolving pattern of cellular horizontal flows (supergranules). Characteristics of the simulated flow pattern match observed characteristics including the velocity power spectrum, cell lifetimes, and cell pattern motion in longitude and latitude. Simulations using an average, and north-south symmetric, meridional motion of the cellular pattern produce polar magnetic fields that are too weak in the North and too strong in the South. Simulations using cellular patterns with meridional motions that evolve with the observed changes in strength and north-south asymmetry will be analyzed to see if they reproduce the polar field evolution observed during the rise of Cycle 24.

Oxygen and the light-dark cycle of nitrogenase activity in two unicellular cyanobacteria.

PubMed

Compaoré, Justine; Stal, Lucas J

2010-01-01

Cyanobacteria capable of fixing dinitrogen exhibit various strategies to protect nitrogenase from inactivation by oxygen. The marine Crocosphaera watsonii WH8501 and the terrestrial Gloeothece sp. PCC6909 are unicellular diazotrophic cyanobacteria that are capable of aerobic nitrogen fixation. These cyanobacteria separate the incompatible processes of oxygenic photosynthesis and nitrogen fixation temporally, confining the latter to the dark. Although these cyanobacteria thrive in fully aerobic environments and can be cultivated diazotrophically under aerobic conditions, the effect of oxygen is not precisely known due to methodological limitations. Here we report the characteristics of nitrogenase activity with respect to well-defined levels of oxygen to which the organisms are exposed, using an online and near real-time acetylene reduction assay combined with sensitive laser-based photoacoustic ethylene detection. The cultures were grown under an alternating 12-12 h light-dark cycle and acetylene reduction was recorded continuously. Acetylene reduction was assayed at 20%, 15%, 10%, 7.5%, 5% and 0% oxygen and at photon flux densities of 30 and 76 mumol m(-2) s(-1) provided at the same light-dark cycle as during cultivation. Nitrogenase activity was predominantly but not exclusively confined to the dark. At 0% oxygen nitrogenase activity in Gloeothece sp. was not detected during the dark and was shifted completely to the light period, while C. watsonii did not exhibit nitrogenase activity at all. Oxygen concentrations of 15% and higher did not support nitrogenase activity in either of the two cyanobacteria. The highest nitrogenase activities were at 5-7.5% oxygen. The highest nitrogenase activities in C. watsonii and Gloeothece sp. were observed at 29 degrees C. At 31 degrees C and above, nitrogenase activity was not detected in C. watsonii while the same was the case at 41 degrees C and above in Gloeothece sp. The differences in the behaviour of nitrogenase activity in these cyanobacteria are discussed with respect to their presumed physiological strategies to protect nitrogenase from oxygen inactivation and to the environment in which they thrive.

Increased capillaries in mitochondrial myopathy: implications for the regulation of oxygen delivery.

PubMed

Taivassalo, Tanja; Ayyad, Karen; Haller, Ronald G

2012-01-01

Human skeletal muscle respiratory chain defects restrict the ability of working muscle to extract oxygen from blood, and result in a hyperkinetic circulation during exercise in which oxygen delivery is excessive relative to oxygen uptake and oxygen levels within contracting muscle are abnormally high. To investigate the role of the muscle microcirculation in this anomalous circulatory response and possible implications for the regulation of muscle angiogenesis, we assessed muscle oxidative capacity during cycle exercise and determined capillary levels and distribution and vascular endothelial growth factor expression in quadriceps muscle biopsies in patients with mitochondrial myopathy attributable to heteroplasmic mitochondrial DNA mutations. We found that in patients with mitochondrial myopathy, muscle capillary levels were twice that of sedentary healthy subjects (3.0 ± 0.9% compared with 1.4 ± 0.3%, P < 0.001) despite the fact that oxygen utilization during peak cycle exercise was half that of control subjects (11.1 ± 4.0 ml/kg/min compared with 20.7 ± 7.9 ml/kg/min, P < 0.01); that capillary area was greatest in patients with the most severe muscle oxidative defects and was more than two times higher around muscle fibre segments with defective (i.e. cytochrome oxidase negative/succinic dehydrogenase-positive or 'ragged-red' fibres) compared with more preserved respiratory chain function; and that vascular endothelial growth factor expression paralleled capillary distribution. The increased muscle capillary levels in patients correlated directly (r(2) = 0.68, P < 0.05) with the severity of the mismatch between systemic oxygen delivery (cardiac output) and oxygen utilization during cycle exercise. Our results suggest that capillary growth is increased as a result of impaired muscle oxidative phosphorylation in mitochondrial myopathy, thus promoting increased blood flow to respiration-incompetent muscle fibres and a mismatch between oxygen delivery and utilization during exercise. Furthermore, the finding of high capillary levels despite elevated tissue oxygen levels during exercise in respiration-deficient muscle fibres implies that mitochondrial metabolism activates angiogenesis in skeletal muscle by a mechanism that is independent of hypoxia.

An advanced lithium-air battery exploiting an ionic liquid-based electrolyte.

PubMed

Elia, G A; Hassoun, J; Kwak, W-J; Sun, Y-K; Scrosati, B; Mueller, F; Bresser, D; Passerini, S; Oberhumer, P; Tsiouvaras, N; Reiter, J

2014-11-12

A novel lithium-oxygen battery exploiting PYR14TFSI-LiTFSI as ionic liquid-based electrolyte medium is reported. The Li/PYR14TFSI-LiTFSI/O2 battery was fully characterized by electrochemical impedance spectroscopy, capacity-limited cycling, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The results of this extensive study demonstrate that this new Li/O2 cell is characterized by a stable electrode-electrolyte interface and a highly reversible charge-discharge cycling behavior. Most remarkably, the charge process (oxygen oxidation reaction) is characterized by a very low overvoltage, enhancing the energy efficiency to 82%, thus, addressing one of the most critical issues preventing the practical application of lithium-oxygen batteries.

Development of a model of atmospheric oxygen variations to estimate terrestrial carbon storage and release

NASA Technical Reports Server (NTRS)

Najjar, Raymond G.; Keeling, Ralph F.; Erickson, David J., III

1995-01-01

Two years of work has been completed towards the development of a model of atmospheric oxygen variations on seasonal to decadal timescales. During the first year we (1) constructed a preliminary monthly-mean climatology of surface ocean oxygen anomalies, (2) began modeling studies to assess the importance of short term variability on the monthly-mean oxygen flux, and (3) conducted preliminary simulations of the annual mean cycle of oxygen in the atmosphere. Most of the second year was devoted to improving the monthly mean climatology of oxygen in the surface ocean.

Mechanisms of Oxidative Stress Resistance in The Brain: Lessons Learned From Hypoxia Tolerant Extremophilic Vertebrates

PubMed Central

Garbarino, Valentina R.; Orr, Miranda E.; Rodriguez, Karl A.; Buffenstein, Rochelle

2016-01-01

The Oxidative Stress Theory of Aging has had tremendous impact in research involving aging and age-associated diseases including those that affect the nervous system. With over half a century of accrued data showing both strong support for and against this theory, there is a need to critically evaluate the data acquired from common biomedical research models, and to also diversify the species used in studies involving this proximate theory. One approach is to follow Orgel’s second axiom that “evolution is smarter than we are” and judiciously choose species that may have evolved to live with chronic or seasonal oxidative stressors. Vertebrates that have naturally evolved to live under extreme conditions (e.g., anoxia or hypoxia), as well as those that undergo daily or seasonal torpor encounter both decreased oxygen availability and subsequent reoxygenation, with concomitant increased oxidative stress. Due to its high metabolic activity, the brain may be particularly vulnerable to oxidative stress. Here, we focus on oxidative stress responses in the brains of certain mouse models as well as extremophilic vertebrates. Exploring the naturally evolved biological tools utilized to cope with seasonal or environmentally variable oxygen availability may yield key information pertinent for how to deal with oxidative stress and thereby mitigate its propagation of age-associated diseases. PMID:25841340

Rangeland health assessment - The key to understanding and assessing rangeland soil health in the Northern Great Plains

USDA-ARS?s Scientific Manuscript database

As the science related to soil and rangeland health evolves, so do their protocols and assessment methodologies. Rangeland health assessments consist of evaluating how well ecological processes such as the water cycle, energy flow and nutrient cycling are functioning at a site. Soil health is the ca...

Chapter 4: Short-Cycle Higher Education in the Netherlands--Adoption and Implementation of the New Associate Degree Qualification

ERIC Educational Resources Information Center

Daale, Hans

2010-01-01

Since 2006, the Netherlands has been actively engaged in a process of developing, piloting, and institutionalizing a new 2-year, short-cycle higher education degree, titled the "associate degree". This initiative evolved as a collaborative grassroots effort spearheaded by several Dutch national higher education and business organizations…

The Evaluation Life Cycle: A Retrospective Assessment of Stages and Phases of the Circles of Care Initiative

ERIC Educational Resources Information Center

Bess, Gary; Allen, James; Deters, Pamela B.

2004-01-01

A life cycle metaphor characterizes the evolving relationship between the evaluator and program staff. This framework suggests that common developmental dynamics occur in roughly the same order across groups and settings. There are stage-specific dynamics that begin with Pre-History, which characterize the relationship between the grantees and…

Nascent life cycles and the emergence of higher-level individuality.

PubMed

Ratcliff, William C; Herron, Matthew; Conlin, Peter L; Libby, Eric

2017-12-05

Evolutionary transitions in individuality (ETIs) occur when formerly autonomous organisms evolve to become parts of a new, 'higher-level' organism. One of the first major hurdles that must be overcome during an ETI is the emergence of Darwinian evolvability in the higher-level entity (e.g. a multicellular group), and the loss of Darwinian autonomy in the lower-level units (e.g. individual cells). Here, we examine how simple higher-level life cycles are a key innovation during an ETI, allowing this transfer of fitness to occur 'for free'. Specifically, we show how novel life cycles can arise and lead to the origin of higher-level individuals by (i) mitigating conflicts between levels of selection, (ii) engendering the expression of heritable higher-level traits and (iii) allowing selection to efficiently act on these emergent higher-level traits. Further, we compute how canonical early life cycles vary in their ability to fix beneficial mutations via mathematical modelling. Life cycles that lack a persistent lower-level stage and develop clonally are far more likely to fix 'ratcheting' mutations that limit evolutionary reversion to the pre-ETI state. By stabilizing the fragile first steps of an evolutionary transition in individuality, nascent higher-level life cycles may play a crucial role in the origin of complex life.This article is part of the themed issue 'Process and pattern in innovations from cells to societies'. © 2017 The Author(s).

A Low-Pressure Oxygen Storage System for Oxygen Supply in Low-Resource Settings.

PubMed

Rassool, Roger P; Sobott, Bryn A; Peake, David J; Mutetire, Bagayana S; Moschovis, Peter P; Black, Jim Fp

2017-12-01

Widespread access to medical oxygen would reduce global pneumonia mortality. Oxygen concentrators are one proposed solution, but they have limitations, in particular vulnerability to electricity fluctuations and failure during blackouts. The low-pressure oxygen storage system addresses these limitations in low-resource settings. This study reports testing of the system in Melbourne, Australia, and nonclinical field testing in Mbarara, Uganda. The system included a power-conditioning unit, a standard oxygen concentrator, and an oxygen store. In Melbourne, pressure and flows were monitored during cycles of filling/emptying, with forced voltage fluctuations. The bladders were tested by increasing pressure until they ruptured. In Mbarara, the system was tested by accelerated cycles of filling/emptying and then run on grid power for 30 d. The low-pressure oxygen storage system performed well, including sustaining a pressure approximately twice the standard working pressure before rupture of the outer bag. Flow of 1.2 L/min was continuously maintained to a simulated patient during 30 d on grid power, despite power failures totaling 2.9% of the total time, with durations of 1-176 min (mean 36.2, median 18.5). The low-pressure oxygen storage system was robust and durable, with accelerated testing equivalent to at least 2 y of operation revealing no visible signs of imminent failure. Despite power cuts, the system continuously provided oxygen, equivalent to the treatment of one child, for 30 d under typical power conditions for sub-Saharan Africa. The low-pressure oxygen storage system is ready for clinical field trials. Copyright © 2017 by Daedalus Enterprises.

Geochemical evidence for cryptic sulfur cycling in salt marsh sediments

NASA Astrophysics Data System (ADS)

Mills, Jennifer V.; Antler, Gilad; Turchyn, Alexandra V.

2016-11-01

Cryptic sulfur cycling is an enigmatic process in which sulfate is reduced to some lower-valence state sulfur species and subsequently quantitatively reoxidized; the rate and microbial energetics of this process and how prevalent it may be in the environment remain controversial. Here we investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through a reductive cycle replacing its oxygen atoms. This cryptic sulfur cycle was replicated in laboratory incubations using 18O-enriched water, demonstrating that the field results do not solely result from mixing processes in the natural environment. Numerical modeling of the laboratory incubations scaled to represent the salt marsh sediments suggests that the uptake rate of sulfate during this cryptic sulfur cycling is similar to the uptake rate of sulfate during the fastest microbial sulfate reduction that has been measured in the natural environment. The difference is that during cryptic sulfur cycling, all of the sulfur is subsequently reoxidized to sulfate. We discuss mechanisms for this pathway of sulfur cycling including the possible link to the subsurface iron cycle.

Evaluation of Eurasian Watermilfoil Control Techniques Using Aquatic Herbicides in Fort Peck Lake, Montana

DTIC Science & Technology

2015-07-01

19 Table 3. Temperature , dissolved oxygen , pH, and wind...21 Table 4. Temperature , dissolved oxygen , and pH measured in the study plots following treatment, Fort Peck Lake, MT, 2012...quality, particularly temperature , pH, dissolved oxygen , and nutrient cycling (Prentki et al. 1979; Carpenter and Lodge 1986, Frodge et al. 1990; Boylen

Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago

PubMed Central

Luo, Genming; Ono, Shuhei; Beukes, Nicolas J.; Wang, David T.; Xie, Shucheng; Summons, Roger E.

2016-01-01

Molecular oxygen (O2) is, and has been, a primary driver of biological evolution and shapes the contemporary landscape of Earth’s biogeochemical cycles. Although “whiffs” of oxygen have been documented in the Archean atmosphere, substantial O2 did not accumulate irreversibly until the Early Paleoproterozoic, during what has been termed the Great Oxygenation Event (GOE). The timing of the GOE and the rate at which this oxygenation took place have been poorly constrained until now. We report the transition (that is, from being mass-independent to becoming mass-dependent) in multiple sulfur isotope signals of diagenetic pyrite in a continuous sedimentary sequence in three coeval drill cores in the Transvaal Supergroup, South Africa. These data precisely constrain the GOE to 2.33 billion years ago. The new data suggest that the oxygenation occurred rapidly—within 1 to 10 million years—and was followed by a slower rise in the ocean sulfate inventory. Our data indicate that a climate perturbation predated the GOE, whereas the relationships among GOE, “Snowball Earth” glaciation, and biogeochemical cycling will require further stratigraphic correlation supported with precise chronologies and paleolatitude reconstructions. PMID:27386544

Diffusive shunting of gases and other molecules in the renal vasculature: physiological and evolutionary significance.

PubMed

Ngo, Jennifer P; Ow, Connie P C; Gardiner, Bruce S; Kar, Saptarshi; Pearson, James T; Smith, David W; Evans, Roger G

2016-11-01

Countercurrent systems have evolved in a variety of biological systems that allow transfer of heat, gases, and solutes. For example, in the renal medulla, the countercurrent arrangement of vascular and tubular elements facilitates the trapping of urea and other solutes in the inner medulla, which in turn enables the formation of concentrated urine. Arteries and veins in the cortex are also arranged in a countercurrent fashion, as are descending and ascending vasa recta in the medulla. For countercurrent diffusion to occur, barriers to diffusion must be small. This appears to be characteristic of larger vessels in the renal cortex. There must also be gradients in the concentration of molecules between afferent and efferent vessels, with the transport of molecules possible in either direction. Such gradients exist for oxygen in both the cortex and medulla, but there is little evidence that large gradients exist for other molecules such as carbon dioxide, nitric oxide, superoxide, hydrogen sulfide, and ammonia. There is some experimental evidence for arterial-to-venous (AV) oxygen shunting. Mathematical models also provide evidence for oxygen shunting in both the cortex and medulla. However, the quantitative significance of AV oxygen shunting remains a matter of controversy. Thus, whereas the countercurrent arrangement of vasa recta in the medulla appears to have evolved as a consequence of the evolution of Henle's loop, the evolutionary significance of the intimate countercurrent arrangement of blood vessels in the renal cortex remains an enigma. Copyright © 2016 the American Physiological Society.

Health effects of metals: a role for evolution?

PubMed Central

Clarkson, T

1995-01-01

Metals have been mined and used since ancient times. The industrial era has seen a sharp increase in both the amounts and variety of metals that find applications in industry. The inadvertent release of metals, such as from fossil fuel consumption, also adds to the global burden. A number of catastrophic outbreaks have alerted us to the occupational and environmental health risks. Life on this planet has evolved in the presence of metals. Cells learned to make use of the more abundant metals in the Archean oceans as an integral component in their structure and function. Today, we inherit these as the essential metals. At the same time, evolving life must have developed means of coping with the potentially toxic actions of metals. The appearance of oxygen in the atmosphere in the Precambrian period also resulted in cells both using and developing protective mechanisms against what must have been a highly toxic, reactive gas. Atmospheric oxygen must have increased the solubility of many metals as insoluble metal sulfides were oxidized to the more soluble sulfates. It may be no coincidence that the protective mechanisms for oxygen are also used to protect against a number of toxic metals. Selected examples are given on the role of evolution in metal toxicology, specifically, examples where the normal function of essential metals is deranged by competition with nonessential metals. Examples are also given of protective mechanisms that involve enzymes or cofactors involved in the oxygen defense system. PMID:7621810

In-plane dissipation maxima and vortex-line distortions in the resistive transitions of oxygen-doped Bi2Sr2CaCu2O(8+delta) single crystals

NASA Astrophysics Data System (ADS)

Hsu, J. W. P.; Mitzi, D. B.; Kapitulnik, A.; Lee, Mark

1991-10-01

Measurements of the in-plane resistive transition of Bi2Sr2CaCu2O(8+delta) single crystals in perpendicular magnetic fields reveal that in oxygen-reduced samples a giant resistance maximum evolves with field. This is not seen in oxygenated samples with similar metallic normal resistivities. As the peak resistivity may exceed the normal resistivity, it cannot arise from ordinary vortex-motion dissipation. A model is proposed where the excess resistance results from nonrigid vortex motion coupling the out-of-plane dissipation to the in-plane resistance at temperatures where pinning effects are negligible.

The complex evaluation of tumor oxygen state and vasculature during preoperative chemotherapy in patients with breast cancer

NASA Astrophysics Data System (ADS)

Pavlov, M. V.; Subochev, P. V.; Kalganova, T. I.; Golubyatnikov, G. Yu.; Plekhanov, V. I.; Ilyinskaya, O. E.; Orlova, A. G.; Shakhova, N. M.; Maslennikova, A. V.

2017-02-01

Effective breast cancer treatment requires the assessment of metabolic changes of tumor tissue during chemo- and hormonotherapy for prediction tumor response. Evaluation of the dynamics of tumor oxygen state (by diffuse optical spectroscopy imaging) and tumor vasculature (by ultrasound investigation in power Doppler mode) was performed before treatment beginning and before the second cycle of chemotherapy in 16 patients who received preoperative chemotherapy. Changes of these indicators were compared then with tumor pathologic response. Breast tumors demonstrated different dynamics of tumor oxygenation depending on the changes of tumor tissue. The increase of the tumor oxygenation after the first cycle of chemotherapy was observed in five of six patients with grade 4 and 5 of pathologic tumor response. Decrease of the oxygenation level was revealed in one patient with the 4th degree of tumor response. Variable changes of the oxygenation level were mentioned in the patients with moderate (the 3d degree) tumor response. Tumor oxygenation decreased or was unchanged in case of 1 or 2 degree of tumor response in five of six cases. The study of the tumor blood vessels didn't reveal any correlation between vasculature changes and tumor response under the performed treatment. The trend of tumor oxygenation in early time after treatment beginning might be a predictive criterion of tumor sensitivity to chemotherapy.

Cycling the Hot CNO: A Teaching Methodology

ERIC Educational Resources Information Center

Frost-Schenk, J. W.; Diget, C. Aa.; Bentley, M. A.; Tuff, A.

2018-01-01

An interactive activity to teach the hot Carbon, Nitrogen and Oxygen (HCNO) cycle is proposed. Justification for why the HCNO cycle is important is included via an example of x-ray bursts. The activity allows teaching and demonstration of half-life, nuclear isotopes, nuclear reactions, protons and a-particles, and catalytic processes. Whilst the…

An ISRU Propellant Production System to Fully Fuel a Mars Ascent Vehicle

NASA Technical Reports Server (NTRS)

Kleinhenz, Julie; Paz, Aaron

2017-01-01

ISRU of Mars resources was base lined in 2009 Design Reference Architecture (DRA) 5.0, but only for Oxygen production using atmospheric CO2The Methane (LCH4) needed for ascent propulsion of the Mars Ascent Vehicle (MAV) would need to be brought from Earth. HOWEVER: Extracting water from the Martian Regolith enables the production of both Oxygen and Methane from Mars resources Water resources could also be used for other applications including: Life support, radiation shielding, plant growth, etc. Water extraction was not base lined in DRA5.0 due to perceived difficulties and complexity in processing regolith. The NASA Evolvable Mars Campaign (EMC) requested studies to look at the quantitative benefits and trades of using Mars water ISRU Phase 1: Examined architecture scenarios for regolith water retrieval. Completed October 2015Phase 2: Deep dive of one architecture concept to look at end-to-end system size, mass, power of a LCH4LO2 ISRU production system.Evolvable Mars CampaignPre-deployed Mars ascent vehicle (MAV)4 crew membersPropellants: Oxygen MethaneGenerate a system model to roll up mass power of a full ISRU system and enable parametric trade studies. Leverage models from previous studies and technology development programs Anchor with mass power performance from existing hardware. Whenever possible used reference-able (published) numbers for traceability.Modular approach to allow subsystem trades and parametric studies. Propellant mass needs taken from most recently published MAV study:Polsgrove, T. et al. (2015), AIAA2015-4416MAV engines operate at mixture ratios (oxygen: methane) between 3:1 and 3.5:1, whereas the Sabatier reactor produces at a 4:1 ratio. Therefore:Methane production is the driving requirement-Excess Oxygen will be produced.

MODELING SEDIMENT-NUTRIENT FLUX AND SEDIMENT OXYGEN DEMAND

EPA Science Inventory

Depositional flux of particulate organic matter in bottom sediments affects nutrients cycling at the sediment-water interface and consumes oxygen from the overlying water in streams, lakes, and estuaries. This project deals with analytical modeling of nitrogen and carbon producti...

TRANSIENT BIOGEOCHEMICAL CYCLING AND SEDIMENT OXYGEN DEMAND

EPA Science Inventory

Through this research, the effects of variable sediment accumulation and oxygen concentration on SOD and soluble chemical fluxes will be quantified. This study will enable correct estimates of “diffuser-induced” SOD to be made that will facilitate appropriate desig...

Liquid oxygen dicting cleaned by falling film method

NASA Technical Reports Server (NTRS)

Paul, H. I.

1967-01-01

Principle of a vertical falling film is used to clean contaminated large diameter and length liquid oxygen /LOX/ cylindrical ducting. The cleaning cycle is performed by flowing trichloroethylene in a falling film down a vertically mounted duct for approximately one hour.

A Causal Relation between Bioluminescence and Oxygen to Quantify the Cell Niche

PubMed Central

Lambrechts, Dennis; Roeffaers, Maarten; Goossens, Karel; Hofkens, Johan; Van de Putte, Tom; Schrooten, Jan; Van Oosterwyck, Hans

2014-01-01

Bioluminescence imaging assays have become a widely integrated technique to quantify effectiveness of cell-based therapies by monitoring fate and survival of transplanted cells. To date these assays are still largely qualitative and often erroneous due to the complexity and dynamics of local micro-environments (niches) in which the cells reside. Here, we report, using a combined experimental and computational approach, on oxygen that besides being a critical niche component responsible for cellular energy metabolism and cell-fate commitment, also serves a primary role in regulating bioluminescent light kinetics. We demonstrate the potential of an oxygen dependent Michaelis-Menten relation in quantifying intrinsic bioluminescence intensities by resolving cell-associated oxygen gradients from bioluminescent light that is emitted from three-dimensional (3D) cell-seeded hydrogels. Furthermore, the experimental and computational data indicate a strong causal relation of oxygen concentration with emitted bioluminescence intensities. Altogether our approach demonstrates the importance of oxygen to evolve towards quantitative bioluminescence and holds great potential for future microscale measurement of oxygen tension in an easily accessible manner. PMID:24840204

Differential expression of survival proteins during decreased intracellular oxygen tension in brain endothelial cells of grey mullets.

PubMed

Ekambaram, Padmini; Narayanan, Meenakshi; Parasuraman, Parimala

2017-02-15

The brain requires constant oxygen supply to perform its biological functions essential for survival. Because of low oxygen capacity and poor oxygen diffusibility of water, many fish species have evolved various adaptive mechanisms to cope with depleted oxygen. Endothelial cells (EC) are the primary components responsible for controlled environment of brain. Brain homeostasis largely depends on integrity of the EC. To elucidate their adaptive strategy, EC were isolated from the fish brain of Kovalam-control site and Ennore estuary-test/field hypoxic site and were subjected to low oxygen tension in laboratory. Cell viability, 4-hydroxynonenal (4HNE) and total antioxidant capacity (TAC) were analyzed to ascertain stress. Hypoxic insult, cytoprotective role of HSPs and apoptotic effect were analyzed by assessing hypoxia-inducible-factor-α (HIF1α), heat-shock-protein-70 (HSP70), heme-oxygenase 1 (HO-1), and apoptosis signal regulating kinase-1 (ASK1). This study evidenced that HSP70 and HO-1 are the key stress proteins, confer high tolerance to decreased oxygen tension mediated stress. Copyright © 2016 Elsevier Ltd. All rights reserved.

A causal relation between bioluminescence and oxygen to quantify the cell niche.

PubMed

Lambrechts, Dennis; Roeffaers, Maarten; Goossens, Karel; Hofkens, Johan; Vande Velde, Greetje; Van de Putte, Tom; Schrooten, Jan; Van Oosterwyck, Hans

2014-01-01

Bioluminescence imaging assays have become a widely integrated technique to quantify effectiveness of cell-based therapies by monitoring fate and survival of transplanted cells. To date these assays are still largely qualitative and often erroneous due to the complexity and dynamics of local micro-environments (niches) in which the cells reside. Here, we report, using a combined experimental and computational approach, on oxygen that besides being a critical niche component responsible for cellular energy metabolism and cell-fate commitment, also serves a primary role in regulating bioluminescent light kinetics. We demonstrate the potential of an oxygen dependent Michaelis-Menten relation in quantifying intrinsic bioluminescence intensities by resolving cell-associated oxygen gradients from bioluminescent light that is emitted from three-dimensional (3D) cell-seeded hydrogels. Furthermore, the experimental and computational data indicate a strong causal relation of oxygen concentration with emitted bioluminescence intensities. Altogether our approach demonstrates the importance of oxygen to evolve towards quantitative bioluminescence and holds great potential for future microscale measurement of oxygen tension in an easily accessible manner.

Biological Effects of the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Schopf, J.

2012-12-01

Fossil evidence of photoautotrophy, documented in Precambrian sediments by stromatolites, stromatolitic microfossils, and carbon isotopic data consistent with autotrophic CO2-fixation, extends to ~3,500 Ma. Such data, however, are insufficient to establish the time of origin of O2-producing (cyanobacterial) photosynthesis from its anoxygenic, photosynthetic bacterial, evolutionary precursor. The oldest (Paleoarchean) stromatolites may have been formed by anoxygenic photoautotrophs, rather than the cyanobacteria that dominate Proterozoic and modern stromatolites. Unlike the cyanobacteria of Proterozoic microbial assemblages, the filamentous and coccoidal microfossils of Archean deposits may represent remnants of non-O2-producing prokaryotes. And although the chemistry of Archean organic matter shows it to be biogenic, its carbon isotopic composition is insufficient to differentiate between oxygenic and anoxygenic sources. Though it is well established that Earth's ecosystem has been based on autotrophy since its early stages and that O2-producing photosynthesis evolved earlier, perhaps much earlier, than the increase of atmospheric oxygen in the ~2,450 and ~2,320 Ma Great Oxidation Event (GOE), the time of origin of oxygenic photoautotrophy has yet to be established. Recent findings suggest that Earth's ecosystem responded more or less immediately to the GOE. The increase of atmospheric oxygen markedly affected ocean water chemistry, most notably by increasing the availability of biologically usable oxygen (which enabled the development of obligate aerobes, such as eukaryotes), and of nitrate, sulfate and hydrogen sulfide (the increase of H2S being a result of microbial reduction of sulfate), the three reactants that power the anaerobic basis of sulfur-cycling microbial sulfuretums. Fossil evidence of the earliest eukaryotes (widely accepted to date from ~1800 Ma and, arguably, ~2200 Ma) fit this scenario, but the most telling example of life's response to the GOE are the new discoveries of fossil sulfuretums of the ~2,300 Ma Kazput Fm. and ~1,800 Ma Duck Creek Fm., both of Western Australia. Both assemblages are cellularly permineralized in deepwater, evidently sub-photic zone cherts, and both are essentially identical in sub-seafloor setting, cobweb-like community fabric, and dominant microbial components to a modern sulfuretum known from anoxic sediments off the coast of Chile. These new findings indicate that not only did life respond to the GOE, but that in a unchanging stable environment -- such as that of the deepwater, evidently sub-photic zone, 2 degrees C, quiescent subsurface anoxic mud inhabited by anaerobic sulfuretums, an ecologic setting that has persisted over billions of years -- the inhabiting microbes remain similarly unchanged, in this instance from 2,300 Ma (Kazput Fm.) to 1,800 Ma (Duck Creek Fm.) to the present (Chilean sulfuretum). To Precambrian paleobiology, these findings are significant, providing biology-based data consistent with the GOE and a new deepwater facies in which to search for evidence of ancient life. But their greatest importance is to Evolutionary Biology, providing firm evidence of the null hypothesis to Darwin's theory of evolution: life evolves as is adapts to changing conditions but, as shown here, there is no evolution if an environment remains constant.

Ignition Temperatures of Metals in Oxygen Atmospheres

NASA Technical Reports Server (NTRS)

Laurendeau, N. M.; Glassman, I.

1971-01-01

The ignition temperature of ten common non-toxic metals has been determined experimentally in an oxygen environment. In this investigation a induction furnace facility that emphasized the preignition surface.oxidation effects upon the ignition temperature was used. The bulk ignition temperatures of barium, bismuth, calcium, iron, lead, magnesium, molybdenum, strontium, tin, and zinc were found and compared to the previous results of Grosse and Conway. The differences in the results are attributed to how the heating cycle is carried out and how the cycle affects the surface oxide coat.

Experimental Results of Integrated Refrigeration and Storage System Testing

NASA Technical Reports Server (NTRS)

Notardonato, W. U.; Johnson, W. L.; Jumper, K.

2009-01-01

Launch operations engineers at the Kennedy Space Center have identified an Integrated Refrigeration and Storage system as a promising technology to reduce launch costs and enable advanced cryogenic operations. This system uses a close cycle Brayton refrigerator to remove energy from the stored cryogenic propellant. This allows for the potential of a zero loss storage and transfer system, as well and control of the state of the propellant through densification or re-liquefaction. However, the behavior of the fluid in this type of system is different than typical cryogenic behavior, and there will be a learning curve associated with its use. A 400 liter research cryostat has been designed, fabricated and delivered to KSC to test the thermo fluid behavior of liquid oxygen as energy is removed from the cryogen by a simulated DC cycle cryocooler. Results of the initial testing phase focusing on heat exchanger characterization and zero loss storage operations using liquid oxygen are presented in this paper. Future plans for testing of oxygen densification tests and oxygen liquefaction tests will also be discussed. KEYWORDS: Liquid Oxygen, Refrigeration, Storage

Durable rechargeable zinc-air batteries with neutral electrolyte and manganese oxide catalyst

NASA Astrophysics Data System (ADS)

Sumboja, Afriyanti; Ge, Xiaoming; Zheng, Guangyuan; Goh, F. W. Thomas; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2016-11-01

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm-2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.

Rice tolerance to suboptimal low temperatures relies on the maintenance of the photosynthetic capacity.

PubMed

Gazquez, Ayelén; Vilas, Juan Manuel; Colman Lerner, Jorge Esteban; Maiale, Santiago Javier; Calzadilla, Pablo Ignacio; Menéndez, Ana Bernardina; Rodríguez, Andrés Alberto

2018-06-01

The purpose of this research was to identify differences between two contrasting rice cultivars in their response to suboptimal low temperatures stress. A transcriptomic analysis of the seedlings was performed and results were complemented with biochemical and physiological analyses. The microarray analysis showed downregulation of many genes related with PSII and particularly with the oxygen evolving complex in the sensitive cultivar IR50. Complementary studies indicated that the PSII performance, the degree of oxygen evolving complex coupling with the PSII core and net photosynthetic rate diminished in this cultivar in response to the stress. However, the tolerant cultivar Koshihikari was able to maintain its energy equilibrium by sustaining the photosynthetic capacity. The increase of oleic acid in Koshihikari could be related with membrane remodelling of the chloroplasts and hence contribute to tolerance. Overall, these results work as a ground for future analyses that look forward to characterize possible mechanisms to tolerate this stress. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Benefits of Mars ISRU Regolith Water Processing: A Case Study for the NASA Evolvable Mars Campaign

NASA Technical Reports Server (NTRS)

Kleinhenz, Julie; Paz, Aaron; Mueller, Robert

2016-01-01

ISRU of Mars resources was baselined in 2009 Design Reference Architecture (DRA) 5.0, but only for Oxygen production using atmospheric CO2. The Methane (LCH4) needed for ascent propulsion of the Mars Ascent Vehicle (MAV) would need to be brought from Earth. However: Extracting water from the Martian Regolith enables the production of both Oxygen and Methane from Mars resources: Water resources could also be used for other applications including: Life support, radiation shielding, plant growth, etc. Water extraction was not baselined in DRA5.0 due to perceived difficulties and complexity in processing regolith. The NASA Evolvable Mars Campaign (EMC) requested studies to look at the quantitative benefits and trades of using Mars water ISRUPhase 1: Examined architecture scenarios for regolith water retrieval. Completed October 2015. Phase 2: Deep dive of one architecture concept to look at end-to-end system size, mass, power of a LCH4/LO2 ISRU production system

X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, J.C.

In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal IImore » EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.« less

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

DOE PAGES

Semin, B. K.; Davletshina, L. N.; Seibert, M.; ...

2017-11-11

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semin, B. K.; Davletshina, L. N.; Seibert, M.

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

Water column biogeochemistry of oxygen minimum zones in the eastern tropical North Atlantic and eastern tropical South Pacific Oceans

NASA Astrophysics Data System (ADS)

Löscher, C. R.; Bange, H. W.; Schmitz, R. A.; Callbeck, C. M.; Engel, A.; Hauss, H.; Kanzow, T.; Kiko, R.; Lavik, G.; Loginova, A.; Melzner, F.; Neulinger, S. C.; Pahlow, M.; Riebesell, U.; Schunck, H.; Thomsen, S.; Wagner, H.

2015-03-01

Recent modeling results suggest that oceanic oxygen levels will decrease significantly over the next decades to centuries in response to climate change and altered ocean circulation. Hence the future ocean may experience major shifts in nutrient cycling triggered by the expansion and intensification of tropical oxygen minimum zones (OMZs). There are numerous feedbacks between oxygen concentrations, nutrient cycling and biological productivity; however, existing knowledge is insufficient to understand physical, chemical and biological interactions in order to adequately assess past and potential future changes. We investigated the pelagic biogeochemistry of OMZs in the eastern tropical North Atlantic and eastern tropical South Pacific during a series of cruise expeditions and mesocosm studies. The following summarizes the current state of research on the influence of low environmental oxygen conditions on marine biota, viruses, organic matter formation and remineralization with a particular focus on the nitrogen cycle in OMZ regions. The impact of sulfidic events on water column biogeochemistry, originating from a specific microbial community capable of highly efficient carbon fixation, nitrogen turnover and N2O production is further discussed. Based on our findings, an important role of sinking particulate organic matter in controlling the nutrient stochiometry of the water column is suggested. These particles can enhance degradation processes in OMZ waters by acting as microniches, with sharp gradients enabling different processes to happen in close vicinity, thus altering the interpretation of oxic and anoxic environments.

Caffeinated nitric oxide-releasing lozenge improves cycling time trial performance.

PubMed

Lee, J; Kim, H T; Solares, G J; Kim, K; Ding, Z; Ivy, J L

2015-02-01

Boosting nitric oxide production during exercise by various means has been found to improve exercise performance. We investigated the effects of a nitric oxide releasing lozenge with added caffeine (70 mg) on oxygen consumption during steady-state exercise and cycling time trial performance using a double-blinded randomized, crossover experimental design. 15 moderately trained cyclists (7 females and 8 males) were randomly assigned to ingest the caffeinated nitric oxide lozenge or placebo 5 min before exercise. Oxygen consumption and blood lactate were assessed at rest and at 50%, 65% and 75% maximal oxygen consumption. Exercise performance was assessed by time to complete a simulated 20.15 km cycling time-trial course. No significant treatment effects for oxygen consumption or blood lactate at rest or during steady-state exercise were observed. However, time-trial performance was improved by 2.1% (p<0.01) when participants consumed the nitric oxide lozenge (2,424±69 s) compared to placebo (2,476±78 s) and without a significant difference in rating of perceived exertion. These results suggest that acute supplementation with a caffeinated nitric oxide releasing lozenge may be a practical and effective means of improving aerobic exercise performance. © Georg Thieme Verlag KG Stuttgart · New York.

Drivers of Variability of Diel-Cycling and Episodic Hypoxia In ...

EPA Pesticide Factsheets

Eutrophication of coastal ecosystems is a longstanding environmental concern, exacerbated by population growth and associated nutrient pollution, and ultimately resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly susceptible to diel-cycling hypoxia, associated with day-night cycles of production and respiration, which can cause extreme excursions in dissolved oxygen (DO) concentrations from anoxia to super-saturation within a single day. Diel oxygen dynamics in these systems are complex, and may be influenced by wind forcing, vertical and horizontal mixing, variation in freshwater inflow, cloud cover, and temperature. To better understand the environmental drivers of periodic hypoxia, this study examined four northern Gulf of Mexico Estuaries (Weeks Bay, AL; Wolf Bay, AL; Fowl River, AL; and St. Louis Bay, MS). Dissolved oxygen varied strongly on a diel basis in all four systems, with periods of sustained low oxygen (>24 h) observed in both Weeks Bay and Wolf Bay. The duration and persistence of hypoxia further varied in response to changing salinity regimes and regional weather. These results underscore the dynamic nature of hypoxia in shallow estuarine systems, and highlight the importance of combining fixed site continuous monitoring data with spatial hydrographic surveys to accurately resolve DO dynamics. This abstract is submitted for presentation at the CERF conference held Nov 8-12 in Oregon

Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bin; Xu, Wu; Tao, Jinhui

Although the rechargeable lithium-oxygen (Li-O2) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon-based air-electrode, Li metal anode, and electrolytes towards reduced oxygen species. Here we demonstrate a simple one-step in-situ electrochemical pre-charging strategy to generate thin protective films on both carbon nanotubes (CNTs) air-electrode and Li metal anode simultaneously under an inert atmosphere. Li-O2 cells after such pre-treatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity-limited protocol of 1000 mAh g-1 and 500 mAh g-1, respectively, which is far more thanmore » those without pre-treatment. The thin-films formed from decomposition of electrolyte during in-situ electrochemical pre-charging process in an inert environment can protect both CNTs air-electrode and Li metal anode prior to conventional Li-O2 discharge/charge cycling where reactive reduced oxygen species are formed. This work provides a new approach for protections of carbon-based air-electrode and Li metal anode in practical Li-O2 batteries, and may also be applied to other battery systems.« less

Exergy analysis of helium liquefaction systems based on modified Claude cycle with two-expanders

NASA Astrophysics Data System (ADS)

Thomas, Rijo Jacob; Ghosh, Parthasarathi; Chowdhury, Kanchan

2011-06-01

Large-scale helium liquefaction systems, being energy-intensive, demand judicious selection of process parameters. An effective tool for design and analysis of thermodynamic cycles for these systems is exergy analysis, which is used to study the behavior of a helium liquefaction system based on modified Claude cycle. Parametric evaluation using process simulator Aspen HYSYS® helps to identify the effects of cycle pressure ratio and expander flow fraction on the exergetic efficiency of the liquefaction cycle. The study computes the distribution of losses at different refrigeration stages of the cycle and helps in selecting optimum cycle pressures, operating temperature levels of expanders and mass flow rates through them. Results from the analysis may help evolving guidelines for designing appropriate thermodynamic cycles for practical helium liquefaction systems.

Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Bruck, A. M.; Sutter, B.; Ming, D. W.; Mahaffy, P.

2014-01-01

A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material

Long-lasting hydrophilicity on nanostructured Si-incorporated diamond-like carbon films.

PubMed

Yi, Jin Woo; Moon, Myoung-Woon; Ahmed, Sk Faruque; Kim, Haeri; Cha, Tae-Gon; Kim, Ho-Young; Kim, Seock-Sam; Lee, Kwang-Ryeol

2010-11-16

We investigated the long-lasting hydrophilic behavior of a Si-incorporated diamond-like carbon (Si-DLC) film by varying the Si fraction in DLC matrix through oxygen and nitrogen plasma surface treatments. The wetting behavior of the water droplets on the pure DLC and Si-DLC with the nitrogen or oxygen plasma treatment revealed that the Si element in the oxygen-plasma-treated Si-DLC films played a major role in maintaining a hydrophilic wetting angle of <10° for 20 days in ambient air. The nanostructured patterns with a roughness of ∼10 nm evolved because of the selective etching of the carbon matrix by the oxygen plasma in the Si-DLC film, where the chemical component of the Si-Ox bond was enriched on the top of the nanopatterns and remained for over 20 days.

On the origins of oxygenic photosynthesis and aerobic respiration in Cyanobacteria.

PubMed

Soo, Rochelle M; Hemp, James; Parks, Donovan H; Fischer, Woodward W; Hugenholtz, Philip

2017-03-31

The origin of oxygenic photosynthesis in Cyanobacteria led to the rise of oxygen on Earth ~2.3 billion years ago, profoundly altering the course of evolution by facilitating the development of aerobic respiration and complex multicellular life. Here we report the genomes of 41 uncultured organisms related to the photosynthetic Cyanobacteria (class Oxyphotobacteria ), including members of the class Melainabacteria and a new class of Cyanobacteria (class Sericytochromatia ) that is basal to the Melainabacteria and Oxyphotobacteria All members of the Melainabacteria and Sericytochromatia lack photosynthetic machinery, indicating that phototrophy was not an ancestral feature of the Cyanobacteria and that Oxyphotobacteria acquired the genes for photosynthesis relatively late in cyanobacterial evolution. We show that all three classes independently acquired aerobic respiratory complexes, supporting the hypothesis that aerobic respiration evolved after oxygenic photosynthesis. Copyright © 2017, American Association for the Advancement of Science.

Sepiapterin Reductase Mediates Chemical Redox Cycling in Lung Epithelial Cells*

PubMed Central

Yang, Shaojun; Jan, Yi-Hua; Gray, Joshua P.; Mishin, Vladimir; Heck, Diane E.; Laskin, Debra L.; Laskin, Jeffrey D.

2013-01-01

In the lung, chemical redox cycling generates highly toxic reactive oxygen species that can cause alveolar inflammation and damage to the epithelium, as well as fibrosis. In this study, we identified a cytosolic NADPH-dependent redox cycling activity in mouse lung epithelial cells as sepiapterin reductase (SPR), an enzyme important for the biosynthesis of tetrahydrobiopterin. Human SPR was cloned and characterized. In addition to reducing sepiapterin, SPR mediated chemical redox cycling of bipyridinium herbicides and various quinones; this activity was greatest for 1,2-naphthoquinone followed by 9,10-phenanthrenequinone, 1,4-naphthoquinone, menadione, and 2,3-dimethyl-1,4-naphthoquinone. Whereas redox cycling chemicals inhibited sepiapterin reduction, sepiapterin had no effect on redox cycling. Additionally, inhibitors such as dicoumarol, N-acetylserotonin, and indomethacin blocked sepiapterin reduction, with no effect on redox cycling. Non-redox cycling quinones, including benzoquinone and phenylquinone, were competitive inhibitors of sepiapterin reduction but noncompetitive redox cycling inhibitors. Site-directed mutagenesis of the SPR C-terminal substrate-binding site (D257H) completely inhibited sepiapterin reduction but had minimal effects on redox cycling. These data indicate that SPR-mediated reduction of sepiapterin and redox cycling occur by distinct mechanisms. The identification of SPR as a key enzyme mediating chemical redox cycling suggests that it may be important in generating cytotoxic reactive oxygen species in the lung. This activity, together with inhibition of sepiapterin reduction by redox-active chemicals and consequent deficiencies in tetrahydrobiopterin, may contribute to tissue injury. PMID:23640889

Cyclic growth in Atlantic region continental crust

NASA Technical Reports Server (NTRS)

Goodwin, A. M.

1986-01-01

Atlantic region continental crust evolved in successive stages under the influence of regular, approximately 400 Ma-long tectonic cycles. Data point to a variety of operative tectonic processes ranging from widespread ocean floor consumption (Wilson cycle) to entirely ensialic (Ampferer-style subduction or simple crustal attenuation-compression). Different processes may have operated concurrently in some or different belts. Resolving this remains the major challenge.

White Flight and the Endless Cycle of Poverty for Urban People of Color in America

ERIC Educational Resources Information Center

Wade, Oscar Syed

2017-01-01

The United States continues to evolve as a divided collection of states, divided by class and race. Despite public policy, legislation and even social unrest, the cycle continues to roll over those disenfranchised populations. This essay is a reflection of the Los Angeles poverty trap, yet applicable to the perpetual poverty faces by blacks and…

Evolution of resource cycling in ecosystems and individuals.

PubMed

Crombach, Anton; Hogeweg, Paulien

2009-06-01

Resource cycling is a defining process in the maintenance of the biosphere. Microbial communities, ranging from simple to highly diverse, play a crucial role in this process. Yet the evolutionary adaptation and speciation of micro-organisms have rarely been studied in the context of resource cycling. In this study, our basic questions are how does a community evolve its resource usage and how are resource cycles partitioned? We design a computational model in which a population of individuals evolves to take up nutrients and excrete waste. The waste of one individual is another's resource. Given a fixed amount of resources, this leads to resource cycles. We find that the shortest cycle dominates the ecological dynamics, and over evolutionary time its length is minimized. Initially a single lineage processes a long cycle of resources, later crossfeeding lineages arise. The evolutionary dynamics that follow are determined by the strength of indirect selection for resource cycling. We study indirect selection by changing the spatial setting and the strength of direct selection. If individuals are fixed at lattice sites or direct selection is low, indirect selection result in lineages that structure their local environment, leading to 'smart' individuals and stable patterns of resource dynamics. The individuals are good at cycling resources themselves and do this with a short cycle. On the other hand, if individuals randomly change position each time step, or direct selection is high, individuals are more prone to crossfeeding: an ecosystem based solution with turbulent resource dynamics, and individuals that are less capable of cycling resources themselves. In a baseline model of ecosystem evolution we demonstrate different eco-evolutionary trajectories of resource cycling. By varying the strength of indirect selection through the spatial setting and direct selection, the integration of information by the evolutionary process leads to qualitatively different results from individual smartness to cooperative community structures.

Results of the Collaborative Energy and Water Cycle Information Services (CEWIS) Workshop on Heterogeneous Dataset Analysis Preparation

NASA Technical Reports Server (NTRS)

Kempler, Steven; Teng, William; Acker, James; Belvedere, Deborah; Liu, Zhong; Leptoukh, Gregory

2010-01-01

In support of the NASA Energy and Water Cycle Study (NEWS), the Collaborative Energy and Water Cycle Information Services (CEWIS), sponsored by NEWS Program Manager Jared Entin, was initiated to develop an evolving set of community-based data and information services that would facilitate users to locate, access, and bring together multiple distributed heterogeneous energy and water cycle datasets. The CEWIS workshop, June 15-16, 2010, at NASA/GSFC, was the initial step of the process, starting with identifying and scoping the issues, as defined by the community.

ALS turbomachinery technology

NASA Technical Reports Server (NTRS)

Csomor, A.; Faulkner, C.; Ferlita, F.

1990-01-01

Advanced Development Programs are being pursued by Rocketdyne, Aerojet, and Pratt and Whitney to define and validate design approaches toward producing low-cost, reliable liquid-hydrogen and liquid-oxygen turbopumps for a 2580 kN (580 klb) thrust Advanced Launch System. The generic approach, which is evolving after 18 months of trade studies and conceptual and preliminary design efforts, is explained. In addition, the preliminary liquid-hydrogen turbopump designs produced in parallel tasks by Rocketdyne and Aerojet and the liquid-oxygen turbopump design produced by Pratt and Whitney are described, and technology features and issues are discussed.

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films

PubMed Central

Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G.; Hayes, Dugan; Kempa, Thomas J.; von Cube, Felix; Bell, David C.; Chen, Lin X.; Nocera, Daniel G.

2017-01-01

Iron doping of nickel oxide films results in enhanced activity for promoting the oxygen evolution reaction (OER). Whereas this enhanced activity has been ascribed to a unique iron site within the nickel oxide matrix, we show here that Fe doping influences the Ni valency. The percent of Fe3+ doping promotes the formation of formal Ni4+, which in turn directly correlates with an enhanced activity of the catalyst in promoting OER. The role of Fe3+ is consistent with its behavior as a superior Lewis acid. PMID:28137835

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G.

2017-01-30

Iron doping of nickel oxide films results in enhanced activity for promoting the oxygen evolution reaction (OER). Whereas this enhanced activity has been ascribed to a unique iron site within the nickel oxide matrix, we show here that Fe doping influences the Ni valency. The percent of Fe3+ doping promotes the formation of formal Ni4+, which in turn directly correlates with an enhanced activity of the catalyst in promoting OER. The role of Fe3+ is consistent with its behavior as a superior Lewis acid.

Electrolytic production of metals using a resistant anode

DOEpatents

Tarcy, G.P.; Gavasto, T.M.; Ray, S.P.

1986-11-04

An electrolytic process is described comprising evolving oxygen on an anode in a molten salt, the anode comprising an alloy comprising a first metal and a second metal, both metals forming oxides, the oxide of the first metal being more resistant than the second metal to attack by the molten salt, the oxide of the second metal being more resistant than the first metal to the diffusion of oxygen. The electrode may also be formed of CuAlO[sub 2] and/or Cu[sub 2]O. 2 figs.

Material Selection Guidelines to Limit Atomic Oxygen Effects on Spacecraft Surfaces

NASA Technical Reports Server (NTRS)

Dooling, D.; Finckenor, M. M.

1999-01-01

This report provides guidelines in selecting materials for satellites and space platforms, designed to operate within the Low-Earth orbit environment, which limit the effects of atomic oxygen interactions with spacecraft surfaces. This document should be treated as an introduction rather than a comprehensive guide since analytical and flight technologies continue to evolve, flight experiments are conducted as primary or piggyback opportunities arise, and our understanding of materials interactions and protection methods grows. The reader is urged to consult recent literature and current web sites containing information about research and flight results.

Modelling coupled turbulence - dissolved oxygen dynamics near the sediment-water interface under wind waves and sea swell.

PubMed

Chatelain, Mathieu; Guizien, Katell

2010-03-01

A one-dimensional vertical unsteady numerical model for diffusion-consumption of dissolved oxygen (DO) above and below the sediment-water interface was developed to investigate DO profile dynamics under wind waves and sea swell (high-frequency oscillatory flows with periods ranging from 2 to 30s). We tested a new approach to modelling DO profiles that coupled an oscillatory turbulent bottom boundary layer model with a Michaelis-Menten based consumption model. The flow regime controls both the mean value and the fluctuations of the oxygen mass transfer efficiency during a wave cycle, as expressed by the non-dimensional Sherwood number defined with the maximum shear velocity (Sh). The Sherwood number was found to be non-dependent on the sediment biogeochemical activity (mu). In the laminar regime, both cycle-averaged and variance of the Sherwood number are very low (Sh <0.05, VAR(Sh)<0.1%). In the turbulent regime, the cycle-averaged Sherwood number is larger (Sh approximately 0.2). The Sherwood number also has intra-wave cycle fluctuations that increase with the wave Reynolds number (VAR(Sh) up to 30%). Our computations show that DO mass transfer efficiency under high-frequency oscillatory flows in the turbulent regime are water-side controlled by: (a) the diffusion time across the diffusive boundary layer and (b) diffusive boundary layer dynamics during a wave cycle. As a result of these two processes, when the wave period decreases, the Sh minimum increases and the Sh maximum decreases. Sh values vary little, ranging from 0.17 to 0.23. For periods up to 30s, oxygen penetration depth into the sediment did not show any intra-wave fluctuations. Values for the laminar regime are small (

40 CFR Appendix Vii to Part 86 - Standard Bench Cycle (SBC)

Code of Federal Regulations, 2012 CFR

2012-07-01

.... VII Appendix VII to Part 86—Standard Bench Cycle (SBC) 1. The standard bench aging durability procedures [Ref. § 86.1823-08(d)] consist of aging a catalyst-oxygen-sensor system on an aging bench which follows the standard bench cycle (SBC) described in this appendix. 2. The SBC requires use of an aging...

40 CFR Appendix Vii to Part 86 - Standard Bench Cycle (SBC)

Code of Federal Regulations, 2014 CFR

2014-07-01

... VII to Part 86—Standard Bench Cycle (SBC) 1. The standard bench aging durability procedures [Ref. § 86.1823-08(d)] consist of aging a catalyst-oxygen-sensor system on an aging bench which follows the standard bench cycle (SBC) described in this appendix. 2. The SBC requires use of an aging bench with an...

40 CFR Appendix Vii to Part 86 - Standard Bench Cycle (SBC)

Code of Federal Regulations, 2013 CFR

2013-07-01

.... VII Appendix VII to Part 86—Standard Bench Cycle (SBC) 1. The standard bench aging durability procedures [Ref. § 86.1823-08(d)] consist of aging a catalyst-oxygen-sensor system on an aging bench which follows the standard bench cycle (SBC) described in this appendix. 2. The SBC requires use of an aging...

Controllable Electrochemical Fabrication of KO2-Decorated Binder-Free Cathodes for Rechargeable Lithium-Oxygen Batteries.

PubMed

Yu, Wei; Wang, Huwei; Qin, Lei; Hu, Junyang; Liu, Liang; Li, Baohua; Zhai, Dengyun; Kang, Feiyu

2018-05-23

Understanding the electrochemical property of superoxides in alkali metal oxygen batteries is critical for the design of a stable oxygen battery with high capacity and long cycle performance. In this work, a KO 2 -decorated binder-free cathode is fabricated by a simple and efficient electrochemical strategy. KO 2 nanoparticles are uniformly coated on the carbon nanotube film (CNT-f) through a controllable discharge process in the K-O 2 battery, and the KO 2 -decorated CNT-f is innovatively introduced into the Li-O 2 battery as the O 2 diffusion electrode. The Li-O 2 battery based on the KO 2 -decorated CNT-f cathode can deliver enhanced discharge capacity, reduced charge overpotential, and more stable cycle performance compared with the battery in the absence of KO 2 . In situ formed KO 2 particles on the surface of CNT-f cathode assist to form Li 2 O 2 nanosheets in the Li-O 2 battery, which contributes to the improvement of discharge capacity and cycle life. Interestingly, the analysis of KO 2 -decorated CNT-f cathodes, after discharge and cycle tests, reveals that the electrochemically synthesized KO 2 seems not a conventional electrocatalyst but a partially dissolvable and decomposable promoter in Li-O 2 batteries.

Evolution of the global phosphorus cycle.

PubMed

Reinhard, Christopher T; Planavsky, Noah J; Gill, Benjamin C; Ozaki, Kazumi; Robbins, Leslie J; Lyons, Timothy W; Fischer, Woodward W; Wang, Chunjiang; Cole, Devon B; Konhauser, Kurt O

2017-01-19

The macronutrient phosphorus is thought to limit primary productivity in the oceans on geological timescales. Although there has been a sustained effort to reconstruct the dynamics of the phosphorus cycle over the past 3.5 billion years, it remains uncertain whether phosphorus limitation persisted throughout Earth's history and therefore whether the phosphorus cycle has consistently modulated biospheric productivity and ocean-atmosphere oxygen levels over time. Here we present a compilation of phosphorus abundances in marine sedimentary rocks spanning the past 3.5 billion years. We find evidence for relatively low authigenic phosphorus burial in shallow marine environments until about 800 to 700 million years ago. Our interpretation of the database leads us to propose that limited marginal phosphorus burial before that time was linked to phosphorus biolimitation, resulting in elemental stoichiometries in primary producers that diverged strongly from the Redfield ratio (the atomic ratio of carbon, nitrogen and phosphorus found in phytoplankton). We place our phosphorus record in a quantitative biogeochemical model framework and find that a combination of enhanced phosphorus scavenging in anoxic, iron-rich oceans and a nutrient-based bistability in atmospheric oxygen levels could have resulted in a stable low-oxygen world. The combination of these factors may explain the protracted oxygenation of Earth's surface over the last 3.5 billion years of Earth history. However, our analysis also suggests that a fundamental shift in the phosphorus cycle may have occurred during the late Proterozoic eon (between 800 and 635 million years ago), coincident with a previously inferred shift in marine redox states, severe perturbations to Earth's climate system, and the emergence of animals.

The deprivation syndrome is the driving force of phylogeny, ontogeny and oncogeny.

PubMed

Heininger, K

2001-01-01

Energy is the motor of life. Energy ensures the organism's survival and competitive advantage for reproductive success. For almost 3 billion years, unicellular organisms were the only life form on earth. Competition for limited energy resources and raw materials exerted an incessant selective pressure on organisms. In the adverse environment and due to their 'feast and famine' life style, hardiness to a variety of stressors, particularly to nutrient deprivation, was the selection principle. Both resistance and mutagenic adaptation to stressors were established as survival strategies by means of context-specific processes creating stability or variability of DNA sequence. The conservation of transduction pathways and functional homology of effector molecules clearly bear witness that the principles of life established during prokaryotic and eukaryotic unicellular evolution, although later diversified, have been unshakably cast to persist during metazoan phylogenesis. A wealth of evidence suggests that unicellular organisms evolved the phenomena of differentiation and apoptosis, sexual reproduction, and even aging, as responses to environmental challenges. These evolutionary accomplishments were elaborated from the dichotomous resistance/mutagenesis response and sophisticated the capacity of cells to tune their genetic information to changing environmental conditions. Notably, the social deprivation responses, differentiation and apoptosis, evolved as intercellularly coordinated events: a multitude of differentiation processes were elaborated from sporulation, the prototypic stress resistance response, while apoptosis, contrary to current concepts, is no altruistic cell suicide but was programmed as a mutagenic survival response; this response, however, is socially thwarted leading into mutagenic error catastrophe. In the hybrid differentiation-apoptosis process, cytocide and cannibalism of apoptotic cells thus serve the purpose of fueling the survival of the selfish genes in the differentiating cells. However, successful mutagenesis, although repressed, persisted in the asocial stress response of carcinogenesis as a regression to primitive unicellular behavior following failure of intercellular communication. While somatic mutagenesis was largely prevented, Metazoa elaborated germ cell mutagenesis as an evolutionary vehicle. Genetic competence, a primitive, stress-induced mating behavior, evolved into sexual reproduction which harnessed mutagenesis by subjecting highly mutable germ cells to a rigid viability selection. These processes were programmatically fixed as life- and cell-cycle events but retained their deprivation response phenotypes. Thus, the differentiation-apoptosis tandem evolved as the 'clay' to mold the specialized structures and functions of a multicellular organism while sexual reproduction elaborated the principle of quality-checked mutagenesis to create the immense diversity of Metazoa following the Cambrian explosion. Throughout these events, reactive oxygen and nitrogen species, which are regulated by energy homeostasis, shape the genetic information in a regulated but random, uncoded process providing the fitness-related feedback of phenotype to genotype. The interplay of genes and environment establishes a dynamic stimulus-response feedback cycle which, in animate nature, may be the organizing principle to contrive the reciprocal duality of energy and matter.

Inhibition of nitrogenase by oxygen in marine cyanobacteria controls the global nitrogen and oxygen cycles

NASA Astrophysics Data System (ADS)

Berman-Frank, I.; Chen, Y.-B.; Gerchman, Y.; Dismukes, G. C.; Falkowski, P. G.

2005-03-01

Cyanobacterial N2-fixation supplies the vast majority of biologically accessible inorganic nitrogen to nutrient-poor aquatic ecosystems. The process, catalyzed by the heterodimeric protein complex, nitrogenase, is thought to predate that of oxygenic photosynthesis. Remarkably, while the enzyme plays such a critical role in Earth's biogeochemical cycles, the activity of nitrogenase in cyanobacteria is markedly inhibited in vivo at a post-translational level by the concentration of O2 in the contemporary atmosphere leading to metabolic and biogeochemical inefficiency in N2 fixation. We illustrate this crippling effect with data from Trichodesmium spp. an important contributor of "new nitrogen" to the world's subtropical and tropical oceans. The enzymatic inefficiency of nitrogenase imposes a major elemental taxation on diazotrophic cyanobacteria both in the costs of protein synthesis and for scarce trace elements, such as iron. This restriction has, in turn, led to a global limitation of fixed nitrogen in the contemporary oceans and provides a strong biological control on the upper bound of oxygen concentration in Earth's atmosphere.

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

PubMed Central

Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

2013-01-01

Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

Effect of oxygen minimum zone formation on communities of marine protists

PubMed Central

Orsi, William; Song, Young C; Hallam, Steven; Edgcomb, Virginia

2012-01-01

Changes in ocean temperature and circulation patterns compounded by human activities are leading to oxygen minimum zone (OMZ) expansion with concomitant alteration in nutrient and climate active trace gas cycling. Here, we report the response of microbial eukaryote populations to seasonal changes in water column oxygen-deficiency using Saanich Inlet, a seasonally anoxic fjord on the coast of Vancouver Island British Columbia, as a model ecosystem. We combine small subunit ribosomal RNA gene sequencing approaches with multivariate statistical methods to reveal shifts in operational taxonomic units during successive stages of seasonal stratification and renewal. A meta-analysis is used to identify common and unique patterns of community composition between Saanich Inlet and the anoxic/sulfidic Cariaco Basin (Venezuela) and Framvaren Fjord (Norway) to show shared and unique responses of microbial eukaryotes to oxygen and sulfide in these three environments. Our analyses also reveal temporal fluctuations in rare populations of microbial eukaryotes, particularly anaerobic ciliates, that may be of significant importance to the biogeochemical cycling of methane in OMZs. PMID:22402396

Monitoring and controlling the dissolved oxygen (DO) concentration within the high aspect ratio vessel (HARV).

PubMed

Saarinen, Mark A; Reece, Julie S; Arnold, Mark A; Murhammer, David W

2003-01-01

A probe-type oxygen sensor was developed utilizing a radioluminescent (RL)-based light source and a ruthenium-based sensing chemistry for monitoring the dissolved oxygen (DO) concentration in a modified version of the NASA-designed high aspect ratio vessel (HARV), a batch rotating wall vessel. This sensor provided the means to monitor the DO concentration in the HARV without influencing the flow pattern, thereby retaining the low shear HARV environment conducive to the formation of 3-dimensional cell aggregates. This sensor lost significant signal as a result of exposure to the first three autoclave cycles, but only minimal change in signal was observed following exposure to subsequent autoclave cycles. A new calibration model requiring only one fitted parameter was developed that accurately fit data over the entire range from 0% to 100% oxygen saturation. The ability for DO concentration control within the vessel was demonstrated by using this sensor to monitor the DO concentration inside the HARV.

CuCr2O4@rGO Nanocomposites as High-Performance Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries

NASA Astrophysics Data System (ADS)

Liu, Jiandi; Zhao, Yanyan; Li, Xin; Wang, Chunge; Zeng, Yaping; Yue, Guanghui; Chen, Qiang

2018-06-01

Rechargeable lithium-oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium-oxygen batteries (LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component. Hence, we aim to demonstrate that CuCr2O4@rGO (CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 200 mA g-1. The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.[Figure not available: see fulltext.

A Novel Layered Sedimentary Rocks Structure of the Oxygen-Enriched Carbon for Ultrahigh-Rate-Performance Supercapacitors.

PubMed

Zhang, Lin-Lin; Li, Huan-Huan; Shi, Yan-Hong; Fan, Chao-Ying; Wu, Xing-Long; Wang, Hai-Feng; Sun, Hai-Zhu; Zhang, Jing-Ping

2016-02-17

In this paper, gelatin as a natural biomass was selected to successfully prepare an oxygen-enriched carbon with layered sedimentary rocks structure, which exhibited ultrahigh-rate performance and excellent cycling stability as supercapacitors. The specific capacitance reached 272.6 F g(-1) at 1 A g(-1) and still retained 197.0 F g(-1) even at 100 A g(-1) (with high capacitance retention of 72.3%). The outstanding electrochemical performance resulted from the special layered structure with large surface area (827.8 m(2) g(-1)) and high content of oxygen (16.215 wt %), which effectively realized the synergistic effects of the electrical double-layer capacitance and pseudocapacitance. Moreover, it delivered an energy density of 25.3 Wh kg(-1) even with a high power density of 34.7 kW kg(-1) and ultralong cycling stability (with no capacitance decay even over 10,000 cycles at 2 A g(-1)) in a symmetric supercapacitor, which are highly desirable for their practical application in energy storage devices and conversion.

Effect of Feeding-Fasting Cycles on Oxygen Consumption and Bioenergetics of Yellow Perch

USGS Publications Warehouse

Chipps, Steven R.; Travis W. Schaeffer,; Daniel E. Spengler,; Casey W. Schoenebeck,; Michael L. Brown,

2012-01-01

We measured growth and oxygen consumption of age-1 yellow perch Perca flavescenssubjected to ad libitum (control) or variable feeding cycles of 2 (i.e., 2 d of feed, 2 d of deprivation), 6, or 12 d for a 72-d period. Individual, female yellow perch (initial weight = 51.9 ± 0.9 g [mean ± SE]) were stocked in 110-L aquaria to provide six replicates per treatment and fed measured rations of live fathead minnow Pimephales promelas. Consumption, absolute growth rate, growth efficiency, and oxygen consumption were similar among feeding regimens. However, growth trajectories for fish on the 2-d cycle were significantly lower than other feed–fast cycles. Hyperphagia occurred in all treatments. Bioenergetics model simulations indicated that consumption was significantly underestimated (t = 5.4, df = 4, P = 0.006), while growth was overestimated (t = −5.5, df = 4, P = 0.005) for fish on the 12-d cycle. However, model errors detected between observed and predicted values were low, ranging from −10.1% to +7.8%. We found that juvenile yellow perch exhibited compensatory growth (CG), but none of the feed–fast treatments resulted in growth overcompensation. Likewise, we found no evidence that respiration rates varied with CG, implying that yellow perch bioenergetics models could be used to predict the effects of feeding history and CG response on food consumption and fish growth.

Large fluctuations of dissolved oxygen in the Indian and Pacific oceans during Dansgaard-Oeschger oscillations caused by variations of North Atlantic Deep Water subduction

NASA Astrophysics Data System (ADS)

Schmittner, Andreas; Galbraith, Eric D.; Hostetler, Steven W.; Pedersen, Thomas F.; Zhang, Rong

2007-09-01

Paleoclimate records from glacial Indian and Pacific oceans sediments document millennial-scale fluctuations of subsurface dissolved oxygen levels and denitrification coherent with North Atlantic temperature oscillations. Yet the mechanism of this teleconnection between the remote ocean basins remains elusive. Here we present model simulations of the oxygen and nitrogen cycles that explain how changes in deepwater subduction in the North Atlantic can cause large and synchronous variations of oxygen minimum zones throughout the Northern Hemisphere of the Indian and Pacific oceans, consistent with the paleoclimate records. Cold periods in the North Atlantic are associated with reduced nutrient delivery to the upper Indo-Pacific oceans, thereby decreasing productivity. Reduced export production diminishes subsurface respiration of organic matter leading to higher oxygen concentrations and less denitrification. This effect of reduced oxygen consumption dominates at low latitudes. At high latitudes in the Southern Ocean and North Pacific, increased mixed layer depths and steepening of isopycnals improve ocean ventilation and oxygen supply to the subsurface. Atmospheric teleconnections through changes in wind-driven ocean circulation modify this basin-scale pattern regionally. These results suggest that changes in the Atlantic Ocean circulation, similar to those projected by climate models to possibly occur in the centuries to come because of anthropogenic climate warming, can have large effects on marine ecosystems and biogeochemical cycles even in remote areas.

The modulation of oxygen vacancies by the combined current effect and temperature cycling in La0.7Sr0.3CoO3 film

NASA Astrophysics Data System (ADS)

Li, J.; Wang, J.; Kuang, H.; Zhao, Y. Y.; Qiao, K. M.; Liu, Y.; Hu, F. X.; Sun, J. R.; Shen, B. G.

2018-05-01

Modulating the oxygen defect concentration has been accepted as an effective method to obtain high catalytic activity in perovskite cobaltites. However, controllably modifying the oxygen vacancy is still a challenge in this type of materials, which strongly obstructs their application. Here, we report a successful oxygen vacancies modulation in the La0.7Sr0.3CoO3 (LSCO) film by using combined current effect and temperature cycling. The temperature dependent transport properties of the LSCO/LAO film were investigated. The results revealed that the resistance of the film keeps increasing under the repeated measurements. It was found that the accumulation of the oxygen vacancy by current effect transforms the Co4+ ion into Co3+ ion, which results in the enhancement of the resistance and thus the transport switching behavior. Moreover, the resistance in the cooling process was found to be much higher than that in previous cooling and heating processes, which indicates that the oxygen escapes more quickly in the high temperature region. On the other hand, our analysis indicates that the CoO6 distortion may contribute to the switching of transport behaviors in the low temperature region. Our work provides an effective and controllable way to modulate oxygen defect in the perovskite-type oxides.

Response of sediment microbial community structure in a freshwater reservoir to manipulations in oxygen availability.

PubMed

Bryant, Lee D; Little, John C; Bürgmann, Helmut

2012-04-01

Hypolimnetic oxygenation systems (HOx) are being increasingly used in freshwater reservoirs to elevate dissolved oxygen levels in the hypolimnion and suppress sediment-water fluxes of soluble metals (e.g. Fe and Mn) which are often microbially mediated. We assessed changes in sediment microbial community structure and corresponding biogeochemical cycling on a reservoir-wide scale as a function of HOx operations. Sediment microbial biomass as quantified by DNA concentration was increased in regions most influenced by the HOx. Following an initial decrease in biomass in the upper sediment while oxygen concentrations were low, biomass typically increased at all depths as the 4-month-long oxygenation season progressed. A distinct shift in microbial community structure was only observed at the end of the season in the upper sediment near the HOx. While this shift was correlated to HOx-enhanced oxygen availability, increased TOC levels and precipitation of Fe- and Mn-oxides, abiotic controls on Fe and Mn cycling, and/or the adaptability of many bacteria to variations in prevailing electron acceptors may explain the delayed response and the comparatively limited changes at other locations. While the sediment microbial community proved remarkably resistant to relatively short-term changes in HOx operations, HOx-induced variation in microbial structure, biomass, and activity was observed after a full season of oxygenation. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Microbial oceanography of anoxic oxygen minimum zones.

PubMed

Ulloa, Osvaldo; Canfield, Donald E; DeLong, Edward F; Letelier, Ricardo M; Stewart, Frank J

2012-10-02

Vast expanses of oxygen-deficient and nitrite-rich water define the major oxygen minimum zones (OMZs) of the global ocean. They support diverse microbial communities that influence the nitrogen economy of the oceans, contributing to major losses of fixed nitrogen as dinitrogen (N(2)) and nitrous oxide (N(2)O) gases. Anaerobic microbial processes, including the two pathways of N(2) production, denitrification and anaerobic ammonium oxidation, are oxygen-sensitive, with some occurring only under strictly anoxic conditions. The detection limit of the usual method (Winkler titrations) for measuring dissolved oxygen in seawater, however, is much too high to distinguish low oxygen conditions from true anoxia. However, new analytical technologies are revealing vanishingly low oxygen concentrations in nitrite-rich OMZs, indicating that these OMZs are essentially anoxic marine zones (AMZs). Autonomous monitoring platforms also reveal previously unrecognized episodic intrusions of oxygen into the AMZ core, which could periodically support aerobic metabolisms in a typically anoxic environment. Although nitrogen cycling is considered to dominate the microbial ecology and biogeochemistry of AMZs, recent environmental genomics and geochemical studies show the presence of other relevant processes, particularly those associated with the sulfur and carbon cycles. AMZs correspond to an intermediate state between two "end points" represented by fully oxic systems and fully sulfidic systems. Modern and ancient AMZs and sulfidic basins are chemically and functionally related. Global change is affecting the magnitude of biogeochemical fluxes and ocean chemical inventories, leading to shifts in AMZ chemistry and biology that are likely to continue well into the future.

Microbial oceanography of anoxic oxygen minimum zones

PubMed Central

Ulloa, Osvaldo; Canfield, Donald E.; DeLong, Edward F.; Letelier, Ricardo M.; Stewart, Frank J.

2012-01-01

Vast expanses of oxygen-deficient and nitrite-rich water define the major oxygen minimum zones (OMZs) of the global ocean. They support diverse microbial communities that influence the nitrogen economy of the oceans, contributing to major losses of fixed nitrogen as dinitrogen (N2) and nitrous oxide (N2O) gases. Anaerobic microbial processes, including the two pathways of N2 production, denitrification and anaerobic ammonium oxidation, are oxygen-sensitive, with some occurring only under strictly anoxic conditions. The detection limit of the usual method (Winkler titrations) for measuring dissolved oxygen in seawater, however, is much too high to distinguish low oxygen conditions from true anoxia. However, new analytical technologies are revealing vanishingly low oxygen concentrations in nitrite-rich OMZs, indicating that these OMZs are essentially anoxic marine zones (AMZs). Autonomous monitoring platforms also reveal previously unrecognized episodic intrusions of oxygen into the AMZ core, which could periodically support aerobic metabolisms in a typically anoxic environment. Although nitrogen cycling is considered to dominate the microbial ecology and biogeochemistry of AMZs, recent environmental genomics and geochemical studies show the presence of other relevant processes, particularly those associated with the sulfur and carbon cycles. AMZs correspond to an intermediate state between two “end points” represented by fully oxic systems and fully sulfidic systems. Modern and ancient AMZs and sulfidic basins are chemically and functionally related. Global change is affecting the magnitude of biogeochemical fluxes and ocean chemical inventories, leading to shifts in AMZ chemistry and biology that are likely to continue well into the future. PMID:22967509

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

USGS Publications Warehouse

Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

2007-01-01

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Emergence of Life on Earth: A Physicochemical Jigsaw Puzzle.

PubMed

Spitzer, Jan

2017-01-01

We review physicochemical factors and processes that describe how cellular life can emerge from prebiotic chemical matter; they are: (1) prebiotic Earth is a multicomponent and multiphase reservoir of chemical compounds, to which (2) Earth-Moon rotations deliver two kinds of regular cycling energies: diurnal electromagnetic radiation and seawater tides. (3) Emerging colloidal phases cyclically nucleate and agglomerate in seawater and consolidate as geochemical sediments in tidal zones, creating a matrix of microspaces. (4) Some microspaces persist and retain memory from past cycles, and others re-dissolve and re-disperse back into the Earth's chemical reservoir. (5) Proto-metabolites and proto-biopolymers coevolve with and within persisting microspaces, where (6) Macromolecular crowding and other non-covalent molecular forces govern the evolution of hydrophilic, hydrophobic, and charged molecular surfaces. (7) The matrices of microspaces evolve into proto-biofilms of progenotes with rudimentary but evolving replication, transcription, and translation, enclosed in unstable cell envelopes. (8) Stabilization of cell envelopes 'crystallizes' bacteria-like genetics and metabolism with low horizontal gene transfer-life 'as we know it.' These factors and processes constitute the 'working pieces' of the jigsaw puzzle of life's emergence. They extend the concept of progenotes as the first proto-cellular life, connected backward in time to the cycling chemistries of the Earth-Moon planetary system, and forward to the ancient cell cycle of first bacteria-like organisms. Supra-macromolecular models of 'compartments first' are preferred: they facilitate macromolecular crowding-a key abiotic/biotic transition toward living states. Evolutionary models of metabolism or genetics 'first' could not have evolved in unconfined and uncrowded environments because of the diffusional drift to disorder mandated by the second law of thermodynamics.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

The indirect electrochemical refining of lunar ores

NASA Technical Reports Server (NTRS)

Semkow, Krystyna W.; Sammells, Anthony F.

1987-01-01

Recent work performed on an electrolytic cell is reported which addresses the implicit limitations in various approaches to refining lunar ores. The cell uses an oxygen vacancy conducting stabilized zirconia solid electrolyte to effect separation between a molten salt catholyte compartment where alkali metals are deposited, and an oxygen-evolving anode of composition La(0.89)Sr(0.1)MnO3. The cell configuration is shown and discussed along with a polarization curve and a steady-state current-voltage curve. In a practical cell, cathodically deposited liquid lithium would be continuously removed from the electrolytic cell and used as a valuable reducing agent for ore refining under lunar conditions. Oxygen would be indirectly electrochemically extracted from lunar ores for breathing purposes.

Three-Body Forces and the Limit of Oxygen Isotopes

NASA Astrophysics Data System (ADS)

Otsuka, Takaharu; Suzuki, Toshio; Holt, Jason D.; Schwenk, Achim; Akaishi, Yoshinori

2010-07-01

The limit of neutron-rich nuclei, the neutron drip line, evolves regularly from light to medium-mass nuclei except for a striking anomaly in the oxygen isotopes. This anomaly is not reproduced in shell-model calculations derived from microscopic two-nucleon forces. Here, we present the first microscopic explanation of the oxygen anomaly based on three-nucleon forces that have been established in few-body systems. This leads to repulsive contributions to the interactions among excess neutrons that change the location of the neutron drip line from O28 to the experimentally observed O24. Since the mechanism is robust and general, our findings impact the prediction of the most neutron-rich nuclei and the synthesis of heavy elements in neutron-rich environments.

Evidence for oxygen vacancies movement during wake-up in ferroelectric hafnium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Starschich, S.; Böttger, U.; Menzel, S.

The wake-up effect which is observed in ferroelectric hafnium oxide is investigated in yttrium doped hafnium oxide prepared by chemical solution deposition. It can be shown that not the amount of cycles but the duration of the applied electrical field is essential for the wake-up. Temperature dependent wake-up cycling in a range of −160 °C to 100 °C reveals a strong temperature activation of the wake-up, which can be attributed to ion rearrangement during cycling. By using asymmetrical electrodes, resistive valence change mechanism switching can be observed coincident with ferroelectric switching. From the given results, it can be concluded that redistribution ofmore » oxygen vacancies is the origin of the wake-up effect.« less

Oxygenation, local muscle oxygen consumption and joint specific power in cycling: the effect of cadence at a constant external work rate.

PubMed

Skovereng, Knut; Ettema, Gertjan; van Beekvelt, Mireille C P

2016-06-01

The present study investigates the effect of cadence on joint specific power and oxygenation and local muscle oxygen consumption in the vastus lateralis and vastus medialis in addition to the relationship between joint specific power and local muscle oxygen consumption (mVO2). Seventeen recreationally active cyclists performed 6 stages of constant load cycling using cadences of 60, 70, 80, 90, 100 and 110 rpm. Joint specific power was calculated using inverse dynamics and mVO2 and oxygenation were measured using near-infrared spectroscopy. Increasing cadence led to increased knee joint power and decreased hip joint power while the ankle joint was unaffected. Increasing cadence also led to an increased deoxygenation in both the vastus lateralis and vastus medialis. Vastus lateralis mVO2 increased when cadence was increased. No effect of cadence was found for vastus medialis mVO2. This study demonstrates a different effect of cadence on the mVO2 of the vastus lateralis and vastus medialis. The combined mVO2 of the vastus lateralis and medialis showed a linear increase with increasing knee joint specific power, demonstrating that the muscles combined related to power generated over the joint.

Cross-validation of Peak Oxygen Consumption Prediction Models From OMNI Perceived Exertion.

PubMed

Mays, R J; Goss, F L; Nagle, E F; Gallagher, M; Haile, L; Schafer, M A; Kim, K H; Robertson, R J

2016-09-01

This study cross-validated statistical models for prediction of peak oxygen consumption using ratings of perceived exertion from the Adult OMNI Cycle Scale of Perceived Exertion. 74 participants (men: n=36; women: n=38) completed a graded cycle exercise test. Ratings of perceived exertion for the overall body, legs, and chest/breathing were recorded each test stage and entered into previously developed 3-stage peak oxygen consumption prediction models. There were no significant differences (p>0.05) between measured and predicted peak oxygen consumption from ratings of perceived exertion for the overall body, legs, and chest/breathing within men (mean±standard deviation: 3.16±0.52 vs. 2.92±0.33 vs. 2.90±0.29 vs. 2.90±0.26 L·min(-1)) and women (2.17±0.29 vs. 2.02±0.22 vs. 2.03±0.19 vs. 2.01±0.19 L·min(-1)) participants. Previously developed statistical models for prediction of peak oxygen consumption based on subpeak OMNI ratings of perceived exertion responses were similar to measured peak oxygen consumption in a separate group of participants. These findings provide practical implications for the use of the original statistical models in standard health-fitness settings. © Georg Thieme Verlag KG Stuttgart · New York.

The Solar Wind Source Cycle: Relationship to Dynamo Behavior

NASA Astrophysics Data System (ADS)

Luhmann, J. G.; Li, Y.; Lee, C. O.; Jian, L. K.; Petrie, G. J. D.; Arge, C. N.

2017-12-01

Solar cycle trends of interest include the evolving properties of the solar wind, the heliospheric medium through which the Sun's plasmas and fields interact with Earth and the planets -including the evolution of CME/ICMEs enroute. Solar wind sources include the coronal holes-the open field regions that constantly evolve with solar magnetic fields as the cycle progresses, and the streamers between them. The recent cycle has been notably important in demonstrating that not all solar cycles are alike when it comes to contributions from these sources, including in the case of ecliptic solar wind. In particular, it has modified our appreciation of the low latitude coronal hole and streamer sources because of their relative prevalence. One way to understand the basic relationship between these source differences and what is happening inside the Sun and on its surface is to use observation-based models like the PFSS model to evaluate the evolution of the coronal field geometry. Although the accuracy of these models is compromised around solar maximum by lack of global surface field information and the sometimes non-potential evolution of the field related to more frequent and widespread emergence of active regions, they still approximate the character of the coronal field state. We use these models to compare the inferred recent cycle coronal holes and streamer belt sources of solar wind with past cycle counterparts. The results illustrate how (still) hemispherically asymmetric weak polar fields maintain a complex mix of low-to-mid latitude solar wind sources throughout the latest cycle, with a related marked asymmetry in the hemispheric distribution of the ecliptic wind sources. This is likely to be repeated until the polar field strength significantly increases relative to the fields at low latitudes, and the latter symmetrize.

Oxygen hypothesis of polar gigantism not supported by performance of Antarctic pycnogonids in hypoxia.

PubMed

Woods, H Arthur; Moran, Amy L; Arango, Claudia P; Mullen, Lindy; Shields, Chris

2009-03-22

Compared to temperate and tropical relatives, some high-latitude marine species are large-bodied, a phenomenon known as polar gigantism. A leading hypothesis on the physiological basis of gigantism posits that, in polar water, high oxygen availability coupled to low metabolic rates relieves constraints on oxygen transport and allows the evolution of large body size. Here, we test the oxygen hypothesis using Antarctic pycnogonids, which have been evolving in very cold conditions (-1.8-0 degrees C) for several million years and contain spectacular examples of gigantism. Pycnogonids from 12 species, spanning three orders of magnitude in body mass, were collected from McMurdo Sound, Antarctica. Individual sea spiders were forced into activity and their performance was measured at different experimental levels of dissolved oxygen (DO). The oxygen hypothesis predicts that, all else being equal, large pycnogonids should perform disproportionately poorly in hypoxia, an outcome that would appear as a statistically significant interaction between body size and oxygen level. In fact, although we found large effects of DO on performance, and substantial interspecific variability in oxygen sensitivity, there was no evidence for sizexDO interactions. These data do not support the oxygen hypothesis of Antarctic pycnogonid gigantism and suggest that explanations must be sought in other ecological or evolutionary processes.

Oxygen hypothesis of polar gigantism not supported by performance of Antarctic pycnogonids in hypoxia

PubMed Central

Woods, H. Arthur; Moran, Amy L.; Arango, Claudia P.; Mullen, Lindy; Shields, Chris

2008-01-01

Compared to temperate and tropical relatives, some high-latitude marine species are large-bodied, a phenomenon known as polar gigantism. A leading hypothesis on the physiological basis of gigantism posits that, in polar water, high oxygen availability coupled to low metabolic rates relieves constraints on oxygen transport and allows the evolution of large body size. Here, we test the oxygen hypothesis using Antarctic pycnogonids, which have been evolving in very cold conditions (−1.8–0°C) for several million years and contain spectacular examples of gigantism. Pycnogonids from 12 species, spanning three orders of magnitude in body mass, were collected from McMurdo Sound, Antarctica. Individual sea spiders were forced into activity and their performance was measured at different experimental levels of dissolved oxygen (DO). The oxygen hypothesis predicts that, all else being equal, large pycnogonids should perform disproportionately poorly in hypoxia, an outcome that would appear as a statistically significant interaction between body size and oxygen level. In fact, although we found large effects of DO on performance, and substantial interspecific variability in oxygen sensitivity, there was no evidence for size×DO interactions. These data do not support the oxygen hypothesis of Antarctic pycnogonid gigantism and suggest that explanations must be sought in other ecological or evolutionary processes. PMID:19129117

The Role of Mitochondrial TCA Cycle Enzymes in Determining Prostate Cancer Chemosensitivity

DTIC Science & Technology

2012-03-01

mitochondrial OAA measurement is performed by a commercial kit from Biovision . Briefly, whole cell lysates or mitochondria fraction were obtained from... Biovision based on the manufacturer protocols. 2) Cellular oxygen consumption and reactive oxygen (ROS) production. One of the metabolic consequences of

Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in Weeks Bay, Alabama.

EPA Science Inventory

Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...

Determining the oxygen isotope composition of evapotranspiration with eddy covariance

USDA-ARS?s Scientific Manuscript database

The oxygen isotope componsition of evapotranspiration (dF) represents an important tracer in the study of biosphere-atmosphere interactions, hydrology, paleoclimate, and carbon cycling. Here we demonstrate direct measurement of dF based on eddy covariance (EC) and tunable diode laser (EC-TDL) techni...

Productivity Estimation of Hypersaline Microbial Mat Communities - Diurnal Cycles of Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Less, G.; Cohen, Y.; Luz, B.; Lazar, B.

2002-05-01

Hypersaline microbial mat communities (MMC) are the modern equivalents of the Archean stromatolities, the first photosynthetic organisms on Earth. An estimate of their oxygen production rate is important to the understanding of oxygen evolution on Earth ca. 2 b.y.b.p. Here we use the diurnal cycle of dissolved oxygen, O2/Ar ratio and the isotopic composition of dissolved oxygen to calculate net and gross primary productivity of MMC growing in a large scale (80 m2) experimental pan. The pan is inoculated with MMC taken from the Solar Lake, Sinai, Egypt and filled with 90\\permil evaporated Red Sea water brine up to a depth of ca. 0.25 m. It is equipped with computerized flow through system that is programmed to pump pan water at selected time intervals into a sampling cell fitted with dissolved oxygen, pH, conductivity and temperature sensors connected to a datalogger. Manual brine samples were taken for calibrating the sensors, mass spectrometric analyses and for measurements of additional relevant parameters. Dissolved oxygen concentrations fluctuate during the diurnal cycle being highly supersaturated except for the end of the night. The O2 curve varies seasonally and has a typical "shark fin" shape due to the MMC metabolic response to the shape of the diurnal light curve. The dissolved oxygen data were fitted to a smooth curve that its time derivative (dO2 /dt) is defined as: Z dO2 /dt=GP-R-k(O2(meas)- O2(sat)) where z is the depth (m); GP and R are the MMC gross production and respiration (mol m-2 d-1), respectively; k is the gas exchange coefficient (m d-1); O2(meas) and O2(sat) (mol L-1) are the measured and equilibrium dissolved oxygen concentrations, respectively. The high resolution sampling of the automated system produces O2 curves that enable the calculation of smooth and reliable time derivatives. The calculations yield net production values that vary between 1,000 10-6 to -100 10-6 mol O2 m-2 h-1 and day respiration rates between 60 10-6 to 30 10-6 mol O2 m-2 h-1 in summer and winter, respectively. Independent estimate of the gross productivity and respiration is provided by the oxygen isotopic measurements.

Miniature fuel cells relieve gas pressure in sealed batteries

NASA Technical Reports Server (NTRS)

Frank, H. A.

1971-01-01

Miniature fuel cells within sealed silver zinc batteries consume evolved hydrogen and oxygen rapidly, preventing pressure rupturing. They do not significantly increase battery weight and they operate in all battery life phases. Complete gas pressure control requires two fuel cells during all phases of operation of silver zinc batteries.

Project Morpheus testing

NASA Image and Video Library

2012-06-25

A frame grab from a mounted video camera on the E-3 Test Stand at Stennis Space Center documents testing of the new Project Morpheus engine. The new liquid methane, liquid oxygen engine will power the Morpheus prototype lander, which could one day evolve to carry cargo safely to the moon, asteroids or Mars surfaces.

Water oxidation: High five iron

NASA Astrophysics Data System (ADS)

Lloret-Fillol, Julio; Costas, Miquel

2016-03-01

The oxidation of water is essential to the sustainable production of fuels using sunlight or electricity, but designing active, stable and earth-abundant catalysts for the reaction is challenging. Now, a complex containing five iron atoms is shown to efficiently oxidize water by mimicking key features of the oxygen-evolving complex in green plants.

Tyrosinase-catalyzed hydroxylation of hydroquinone, a depigmenting agent, to hydroxyhydroquinone: A kinetic study.

PubMed

García-Molina, María del Mar; Muñoz Muñoz, Jose Luis; Martinez-Ortiz, Francisco; Martinez, José Rodriguez; García-Ruiz, Pedro Antonio; Rodriguez-López, José Neptuno; García-Cánovas, Francisco

2014-07-01

Hydroquinone (HQ) is used as a depigmenting agent. In this work we demonstrate that tyrosinase hydroxylates HQ to 2-hydroxyhydroquinone (HHQ). Oxy-tyrosinase hydroxylates HQ to HHQ forming the complex met-tyrosinase-HHQ, which can evolve in two different ways, forming deoxy-tyrosinase and p-hydroxy-o-quinone, which rapidly isomerizes to 2-hydroxy-p-benzoquinone or on the other way generating met-tyrosinase and HHQ. In the latter case, HHQ is rapidly oxidized by oxygen to generate 2-hydroxy-p-benzoquinone, and therefore, it cannot close the enzyme catalytic cycle for the lack of reductant (HHQ). However, in the presence of hydrogen peroxide, met-tyrosinase (inactive on hydroquinone) is transformed into oxy-tyrosinase, which is active on HQ. Similarly, in the presence of ascorbic acid, HQ is transformed into 2-hydroxy-p-benzoquinone by the action of tyrosinase; however, in this case, ascorbic acid reduces met-tyrosinase to deoxy-tyrosinase, which after binding to oxygen, originates oxy-tyrosinase. This enzymatic form is now capable of reacting with HQ to generate p-hydroxy-o-quinone, which rapidly isomerizes to 2-hydroxy-p-benzoquinone. The formation of HHQ during the action of tyrosinase on HQ is demonstrated by means of high performance liquid chromatography mass spectrometry (HPLC-MS) by using hydrogen peroxide and high ascorbic acid concentrations. We propose a kinetic mechanism for the tyrosinase oxidation of HQ which allows us the kinetic characterization of the process. A possible explanation of the cytotoxic effect of HQ is discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Serial time-resolved crystallography of photosystem II using a femtosecond X-ray laser

PubMed Central

Kupitz, Christopher; Basu, Shibom; Grotjohann, Ingo; Fromme, Raimund; Zatsepin, Nadia A.; Rendek, Kimberly N.; Hunter, Mark S.; Shoeman, Robert L.; White, Thomas A.; Wang, Dingjie; James, Daniel; Yang, Jay-How; Cobb, Danielle E.; Reeder, Brenda; Sierra, Raymond G.; Liu, Haiguang; Barty, Anton; Aquila, Andrew L.; Deponte, Daniel; Kirian, Richard A.; Bari, Sadia; Bergkamp, Jesse J.; Beyerlein, Kenneth R.; Bogan, Michael J.; Caleman, Carl; Chao, Tzu-Chiao; Conrad, Chelsie E.; Davis, Katherine M.; Fleckenstein, Holger; Galli, Lorenzo; Hau-Riege, Stefan P.; Kassemeyer, Stephan; Laksmono, Hartawan; Liang, Mengning; Lomb, Lukas; Marchesini, Stefano; Martin, Andrew V.; Messerschmidt, Marc; Milathianaki, Despina; Nass, Karol; Ros, Alexandra; Roy-Chowdhury, Shatabdi; Schmidt, Kevin; Seibert, Marvin; Steinbrener, Jan; Stellato, Francesco; Yan, Lifen; Yoon, Chunhong; Moore, Thomas A.; Moore, Ana L.; Pushkar, Yulia; Williams, Garth J.; Boutet, Sébastien; Doak, R. Bruce; Weierstall, Uwe; Frank, Matthias; Chapman, Henry N.; Spence, John C. H.; Fromme, Petra

2015-01-01

Photosynthesis, a process catalysed by plants, algae and cyanobacteria converts sunlight to energy thus sustaining all higher life on Earth. Two large membrane protein complexes, photosystem I and II (PSI and PSII), act in series to catalyse the light-driven reactions in photosynthesis. PSII catalyses the light-driven water splitting process, which maintains the Earth’s oxygenic atmosphere1. In this process, the oxygen-evolving complex (OEC) of PSII cycles through five states, S0 to S4, in which four electrons are sequentially extracted from the OEC in four light-driven charge-separation events. Here we describe time resolved experiments on PSII nano/microcrystals from Thermosynechococcus elongatus performed with the recently developed2 technique of serial femtosecond crystallography. Structures have been determined from PSII in the dark S1 state and after double laser excitation (putative S3 state) at 5 and 5.5 Å resolution, respectively. The results provide evidence that PSII undergoes significant conformational changes at the electron acceptor side and at the Mn4CaO5 core of the OEC. These include an elongation of the metal cluster, accompanied by changes in the protein environment, which could allow for binding of the second substrate water molecule between the more distant protruding Mn (referred to as the ‘dangler’ Mn) and the Mn3CaOx cubane in the S2 to S3 transition, as predicted by spectroscopic and computational studies3,4. This work shows the great potential for time-resolved serial femtosecond crystallography for investigation of catalytic processes in biomolecules. PMID:25043005

Differential temperature effects on dissipation of excess light energy and energy partitioning in lut2 mutant of Arabidopsis thaliana under photoinhibitory conditions.

PubMed

Popova, Antoaneta V; Dobrev, Konstantin; Velitchkova, Maya; Ivanov, Alexander G

2018-05-03

The high-light-induced alterations in photosynthetic performance of photosystem II (PSII) and photosystem I (PSI) as well as effectiveness of dissipation of excessive absorbed light during illumination for different periods of time at room (22 °C) and low (8-10 °C) temperature of leaves of Arabidopsis thaliana, wt and lut2, were followed with the aim of unraveling the role of lutein in the process of photoinhibition. Photosynthetic parameters of PSII and PSI were determined on whole leaves by PAM fluorometer and oxygen evolving activity-by a Clark-type electrode. In thylakoid membranes, isolated from non-illuminated and illuminated for 4.5 h leaves of wt and lut2 the photochemical activity of PSII and PSI and energy interaction between the main pigment-protein complexes was determined. Results indicate that in non-illuminated leaves of lut2 the maximum rate of oxygen evolution and energy utilization in PSII is lower, excitation pressure of PSII is higher and cyclic electron transport around PSI is faster than in wt leaves. Under high-light illumination, lut2 leaves are more sensitive in respect to PSII performance and the extent of increase of excitation pressure of PSII, Φ NO , and cyclic electron transport around PSI are higher than in wt leaves, especially when illumination is performed at low temperature. Significant part of the excessive light energy is dissipated via mechanism, not dependent on ∆pH and to functioning of xanthophyll cycle in LHCII, operating more intensively in lut2 leaves.

Redox signaling and stress tolerance in plants: a focus on vitamin E.

PubMed

Miret, Javier A; Munné-Bosch, Sergi

2015-03-01

Plants are subject to specific redox processes, in which photosynthesis plays a prominent role. Chloroplasts function in light at high oxygen tensions and are enormous generators of reactive oxygen species, mainly singlet oxygen. This side product of photosynthesis inflicts damage to thylakoid membranes at high concentrations, but at the same time it is an essential component of cellular signaling. Detoxification of singlet oxygen is achieved by different means, including quenching and scavenging by tocopherols, responsible for controlling singlet oxygen levels, and the extent of lipid peroxidation in chloroplasts. Here, environmental conditions leading to excess light in chloroplasts will be used to show the importance of singlet oxygen, tocopherols, and lipid peroxidation in cell signaling. Defects in antioxidant protection (e.g., tocopherol deficiency) can lead to increased photo-oxidative damage, but also to the activation of defense pathways, illustrating the phenotypic plasticity evolved by plants to withstand stress. Most importantly, these studies show how redox signaling processes are integrated within the cell and illustrate the great capacity of plants to adapt to their environment. © 2015 New York Academy of Sciences.

Modelling hourly dissolved oxygen concentration (DO) using dynamic evolving neural-fuzzy inference system (DENFIS)-based approach: case study of Klamath River at Miller Island Boat Ramp, OR, USA.

PubMed

Heddam, Salim

2014-01-01

In this study, we present application of an artificial intelligence (AI) technique model called dynamic evolving neural-fuzzy inference system (DENFIS) based on an evolving clustering method (ECM), for modelling dissolved oxygen concentration in a river. To demonstrate the forecasting capability of DENFIS, a one year period from 1 January 2009 to 30 December 2009, of hourly experimental water quality data collected by the United States Geological Survey (USGS Station No: 420853121505500) station at Klamath River at Miller Island Boat Ramp, OR, USA, were used for model development. Two DENFIS-based models are presented and compared. The two DENFIS systems are: (1) offline-based system named DENFIS-OF, and (2) online-based system, named DENFIS-ON. The input variables used for the two models are water pH, temperature, specific conductance, and sensor depth. The performances of the models are evaluated using root mean square errors (RMSE), mean absolute error (MAE), Willmott index of agreement (d) and correlation coefficient (CC) statistics. The lowest root mean square error and highest correlation coefficient values were obtained with the DENFIS-ON method. The results obtained with DENFIS models are compared with linear (multiple linear regression, MLR) and nonlinear (multi-layer perceptron neural networks, MLPNN) methods. This study demonstrates that DENFIS-ON investigated herein outperforms all the proposed techniques for DO modelling.

Purification and characterization of an oxygen-evolving photosystem II from Leptolyngbya sp. strain O-77.

PubMed

Nakamori, Harutaka; Yatabe, Takeshi; Yoon, Ki-Seok; Ogo, Seiji

2014-08-01

A new cyanobacterium of strain O-77 was isolated from a hot spring at Aso-Kuju National Park, Kumamoto, Japan. According to the phylogenetic analysis determined by 16S rRNA gene sequence, the strain O-77 belongs to the genus Leptolyngbya, classifying into filamentous non-heterocystous cyanobacteria. The strain O-77 showed the thermophilic behavior with optimal growth temperature of 55°C. Moreover, we have purified and characterized the oxygen-evolving photosystem II (PSII) from the strain O-77. The O2-evolving activity of the purified PSII from strain O-77 (PSIIO77) was 1275 ± 255 μmol O2 (mg Chl a)(-1) h(-1). Based on the results of MALDI-TOF mass spectrometry and urea-SDS-PAGE analysis, the purified PSIIO77 was composite of the typical PSII components of CP47, CP43, PsbO, D2, D1, PsbV, PsbQ, PsbU, and several low molecular mass subunits. Visible absorption and 77 K fluorescence spectra of the purified PSIIO77 were almost identical to those of other purified PSIIs from cyanobacteria. This report provides the successful example for the purification and characterization of an active PSII from thermophilic, filamentous non-heterocystous cyanobacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Fish Ecology and Evolution in the World's Oxygen Minimum Zones and Implications of Ocean Deoxygenation.

PubMed

Gallo, N D; Levin, L A

Oxygen minimum zones (OMZs) and oxygen limited zones (OLZs) are important oceanographic features in the Pacific, Atlantic, and Indian Ocean, and are characterized by hypoxic conditions that are physiologically challenging for demersal fish. Thickness, depth of the upper boundary, minimum oxygen levels, local temperatures, and diurnal, seasonal, and interannual oxycline variability differ regionally, with the thickest and shallowest OMZs occurring in the subtropics and tropics. Although most fish are not hypoxia-tolerant, at least 77 demersal fish species from 16 orders have evolved physiological, behavioural, and morphological adaptations that allow them to live under the severely hypoxic, hypercapnic, and at times sulphidic conditions found in OMZs. Tolerance to OMZ conditions has evolved multiple times in multiple groups with no single fish family or genus exploiting all OMZs globally. Severely hypoxic conditions in OMZs lead to decreased demersal fish diversity, but fish density trends are variable and dependent on region-specific thresholds. Some OMZ-adapted fish species are more hypoxia-tolerant than most megafaunal invertebrates and are present even when most invertebrates are excluded. Expansions and contractions of OMZs in the past have affected fish evolution and diversity. Current patterns of ocean warming are leading to ocean deoxygenation, causing the expansion and shoaling of OMZs, which is expected to decrease demersal fish diversity and alter trophic pathways on affected margins. Habitat compression is expected for hypoxia-intolerant species, causing increased susceptibility to overfishing for fisheries species. Demersal fisheries are likely to be negatively impacted overall by the expansion of OMZs in a warming world. © 2016 Elsevier Ltd. All rights reserved.

Temperature-sensitive PSII: a novel approach for sustained photosynthetic hydrogen production.

PubMed

Bayro-Kaiser, Vinzenz; Nelson, Nathan

2016-12-01

The need for energy and the associated burden are ever growing. It is crucial to develop new technologies for generating clean and efficient energy for society to avoid upcoming energetic and environmental crises. Sunlight is the most abundant source of energy on the planet. Consequently, it has captured our interest. Certain microalgae possess the ability to capture solar energy and transfer it to the energy carrier, H 2 . H 2 is a valuable fuel, because its combustion produces only one by-product: water. However, the establishment of an efficient biophotolytic H 2 production system is hindered by three main obstacles: (1) the hydrogen-evolving enzyme, [FeFe]-hydrogenase, is highly sensitive to oxygen; (2) energy conversion efficiencies are not economically viable; and (3) hydrogen-producing organisms are sensitive to stressful conditions in large-scale production systems. This study aimed to circumvent the oxygen sensitivity of this process with a cyclic hydrogen production system. This approach required a mutant that responded to high temperatures by reducing oxygen evolution. To that end, we randomly mutagenized the green microalgae, Chlamydomonas reinhardtii, to generate mutants that exhibited temperature-sensitive photoautotrophic growth. The selected mutants were further characterized by their ability to evolve oxygen and hydrogen at 25 and 37 °C. We identified four candidate mutants for this project. We characterized these mutants with PSII fluorescence, P700 absorbance, and immunoblotting analyses. Finally, we demonstrated that these mutants could function in a prototype hydrogen-producing bioreactor. These mutant microalgae represent a novel approach for sustained hydrogen production.

Effect of Short-Term, High-Intensity Exercise on Anaerobic Threshold in Women.

ERIC Educational Resources Information Center

Evans, Blanche W.

This study investigated the effects of a six-week, high-intensity cycling program on anaerobic threshold (AT) in ten women. Subjects trained four days a week using high-intensity interval-type cycle exercises. Workouts included six 4-minute intervals cycling at 85 percent maximal oxygen uptake (VO sub 2 max), separated by 3-minute intervals of…

Evolution of cyclic mixmaster universes with noncomoving radiation

NASA Astrophysics Data System (ADS)

Ganguly, Chandrima; Barrow, John D.

2017-12-01

We study a model of a cyclic, spatially homogeneous, anisotropic, "mixmaster" universe of Bianchi type IX, containing a radiation field with noncomoving ("tilted" with respect to the tetrad frame of reference) velocities and vorticity. We employ a combination of numerical and approximate analytic methods to investigate the consequences of the second law of thermodynamics on the evolution. We model a smooth cycle-to-cycle evolution of the mixmaster universe, bouncing at a finite minimum, by the device of adding a comoving "ghost" field with negative energy density. In the absence of a cosmological constant, an increase in entropy, injected at the start of each cycle, causes an increase in the volume maxima, increasing approach to flatness, falling velocities and vorticities, and growing anisotropy at the expansion maxima of successive cycles. We find that the velocities oscillate rapidly as they evolve and change logarithmically in time relative to the expansion volume. When the conservation of momentum and angular momentum constraints are imposed, the spatial components of these velocities fall to smaller values when the entropy density increases, and vice versa. Isotropization is found to occur when a positive cosmological constant is added because the sequence of oscillations ends and the dynamics expand forever, evolving towards a quasi-de Sitter asymptote with constant velocity amplitudes. The case of a single cycle of evolution with a negative cosmological constant added is also studied.

SN 2010LP—A TYPE IA SUPERNOVA FROM A VIOLENT MERGER OF TWO CARBON-OXYGEN WHITE DWARFS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kromer, M.; Taubenberger, S.; Seitenzahl, I. R.

2013-11-20

SN 2010lp is a subluminous Type Ia supernova (SN Ia) with slowly evolving lightcurves. Moreover, it is the only subluminous SN Ia observed so far that shows narrow emission lines of [O I] in late-time spectra, indicating unburned oxygen close to the center of the ejecta. Most explosion models for SNe Ia cannot explain the narrow [O I] emission. Here, we present hydrodynamic explosion and radiative transfer calculations showing that the violent merger of two carbon-oxygen white dwarfs of 0.9 and 0.76 M {sub ☉} adequately reproduces the early-time observables of SN 2010lp. Moreover, our model predicts oxygen close tomore » the center of the explosion ejecta, a pre-requisite for narrow [O I] emission in nebular spectra as observed in SN 2010lp.« less

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1990-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

PubMed

Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

2014-08-15

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. This journal is © The Royal Society of Chemistry 2012

Boom and bust in continuous time evolving economic model

NASA Astrophysics Data System (ADS)

Mitchell, L.; Ackland, G. J.

2009-08-01

We show that a simple model of a spatially resolved evolving economic system, which has a steady state under simultaneous updating, shows stable oscillations in price when updated asynchronously. The oscillations arise from a gradual decline of the mean price due to competition among sellers competing for the same resource. This lowers profitability and hence population but is followed by a sharp rise as speculative sellers invade the large un-inhabited areas. This cycle then begins again.

Empirical Records of Environmental Change across the Archean-Proterozoic Transition

NASA Astrophysics Data System (ADS)

Kaufman, A. J.

2011-12-01

Time-series geochemical analyses of scientific drill cores intersecting the Archean-Proterozoic transition suggest a coupling of environmental and biological change that culminated in the pervasive oxygenation of Earth's atmosphere and oceans. Elemental and multiple isotope measurements of sedimentary archives, including carbonate, shale, and banded iron-formation from Western Australia, South Africa, Brazil, and southern Canada, indicate important changes in the carbon, sulfur, and nitrogen cycles that monitor the redox state of the oceans and the cyanobacterial buildup of atmospheric oxygen and ozone. In response, continental weathering would have increased, resulting in the enhanced delivery of sulfate and nutrients to seawater, further stimulating photoautotrophic fluxes of oxygen to surface environments. The positive feedback may additionally be responsible for the decline of atmospheric methane and surface refrigeration, represented by a series of discrete ice ages beginning around 2.4 billion years ago, due to the loss of greenhouse capacity during a time of lower solar luminosity. While speculative, the linkage of surface oxidation with enhanced nutrient supply and development of stratospheric sunscreen soon after the Archean-Proterozoic boundary suggests that the earliest perturbation in the carbon cycle may be associated with the rapid expansion of single-celled eukaryotes. Both sterol synthesis in eukaryotes and aerobic respiration require significant levels of oxygen in the ambient environment. Hence, Earth's earliest ice age(s) and onset of a modern and far more energetic carbon cycle may have been directly related to the global expansion of cyanobacteria that released oxygen to the environment, and of eukaryotes that respired it.

Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

PubMed Central

Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

1984-01-01

Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

Enhanced Lithium Oxygen Battery Using a Glyme Electrolyte and Carbon Nanotubes.

PubMed

Carbone, Lorenzo; Moro, Paolo Tomislav; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steven G; Hassoun, Jusef

2018-05-16

The lithium oxygen battery has a theoretical energy density potentially meeting the challenging requirements of electric vehicles. However, safety concerns and short lifespan hinder its application in practical systems. In this work, we show a cell configuration, including a multiwalled carbon nanotube electrode and a low flammability glyme electrolyte, capable of hundreds of cycles without signs of decay. Nuclear magnetic resonance and electrochemical tests confirm the suitability of the electrolyte in a practical battery, whereas morphological and structural aspects revealed by electron microscopy and X-ray diffraction demonstrate the reversible formation and dissolution of lithium peroxide during the electrochemical process. The enhanced cycle life of the cell and the high safety of the electrolyte suggest the lithium oxygen battery herein reported as a viable system for the next generation of high-energy applications.

Study on performances of colorless and transparent shape memory polyimide film in space thermal cycling, atomic oxygen and ultraviolet irradiation environments

NASA Astrophysics Data System (ADS)

Gao, Hui; Lan, Xin; Liu, Liwu; Xiao, Xinli; Liu, Yanju; Leng, Jinsong

2017-09-01

Shape memory polymers with high glass transition temperature (HSMPs) and HSMP-based deployable structures and devices, which can bear harsh operation conditions for durable applications, have attracted more and more interest in recent years. In this article, colorless and transparent shape memory polyimide (SMCTPI) films were subjected to simulated vacuum thermal cycling, atomic oxygen (AO) and ultraviolet (UV) irradiation environments up to 600 h, 556 h and 600 h for accelerated irradiation. The glass transition temperature (Tg) determined by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) had no obvious changes after being irradiated by varying amounts of thermal cycling, AO and UV irradiation dose. After being irradiated by 50 thermal cycles, 10 × 1021 atoms cm-2 AO irradiation and 3000 ESH UV irradiation, shape recovery behaviors of SMCTPI films also had no obvious damage even if they experienced 30 shape memory cycles, while the surface morphologies and optical properties were seriously destroyed by AO irradiation, as compared with thermal cycling and UV irradiation. The tensile strength could separately maintain 122 MPa, 120 MPa and 70 MPa after 50 thermal cycles, 10 × 1021 atoms cm-2 AO irradiation and 3000 ESH UV irradiation, which shows great potential for use in aerospace structures and devices.

A Water-/Fireproof Flexible Lithium-Oxygen Battery Achieved by Synergy of Novel Architecture and Multifunctional Separator.

PubMed

Yin, Yan-Bin; Yang, Xiao-Yang; Chang, Zhi-Wen; Zhu, Yun-Hai; Liu, Tong; Yan, Jun-Min; Jiang, Qing

2018-01-01

To meet the increasing demands for portable and flexible devices in a rapidly developing society, it is urgently required to develop highly safe and flexible electrochemical energy-storage systems. Flexible lithium-oxygen batteries with high theoretical specific energy density are promising candidates; however, the conventional half-open structure design prevents it from working properly under water or fire conditions. Herein, as a proof-of-concept experiment, a highly safe flexible lithium-oxygen battery achieved by the synergy of a vital multifunctional structure design and a unique composite separator is proposed and fabricated. The structure can effectively prevent the invasion of water from the environment and combustion, which is further significantly consolidated with the help of a polyimide and poly(vinylidene fluoride-co-hexafluoropropylene) composite separator, which holds good water resistance, thermal stability, and ionic conductivity. Unexpectedly, the obtained lithium-oxygen battery exhibits superior flexibility, water resistance, thermal resistance, and cycling stability (up to 218 cycles; at a high current of 1 mA and capacity of 4 mA h). This novel water/fireproof, flexible lithium-oxygen battery is a promising candidate to power underwater flexible electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cis-Lunar Reusable In-Space Transportation Architecture for the Evolvable Mars Campaign

NASA Technical Reports Server (NTRS)

McVay, Eric S.; Jones, Christopher A.; Merrill, Raymond G.

2016-01-01

Human exploration missions to Mars or other destinations in the solar system require large quantities of propellant to enable the transportation of required elements from Earth's sphere of influence to Mars. Current and proposed launch vehicles are incapable of launching all of the requisite mass on a single vehicle; hence, multiple launches and in-space aggregation are required to perform a Mars mission. This study examines the potential of reusable chemical propulsion stages based in cis-lunar space to meet the transportation objectives of the Evolvable Mars Campaign and identifies cis-lunar propellant supply requirements. These stages could be supplied with fuel and oxidizer delivered to cis-lunar space, either launched from Earth or other inner solar system sources such as the Moon or near Earth asteroids. The effects of uncertainty in the model parameters are evaluated through sensitivity analysis of key parameters including the liquid propellant combination, inert mass fraction of the vehicle, change in velocity margin, and change in payload masses. The outcomes of this research include a description of the transportation elements, the architecture that they enable, and an option for a campaign that meets the objectives of the Evolvable Mars Campaign. This provides a more complete understanding of the propellant requirements, as a function of time, that must be delivered to cis-lunar space. Over the selected sensitivity ranges for the current payload and schedule requirements of the 2016 point of departure of the Evolvable Mars Campaign destination systems, the resulting propellant delivery quantities are between 34 and 61 tonnes per year of hydrogen and oxygen propellant, or between 53 and 76 tonnes per year of methane and oxygen propellant, or between 74 and 92 tonnes per year of hypergolic propellant. These estimates can guide future propellant manufacture and/or delivery architectural analysis.

Effect of micro-oxygenation and wood type on the phenolic composition and color of an aged red wine.

PubMed

Sánchez-Iglesias, Montserrat; González-Sanjosé, Ma Luisa; Pérez-Magariño, Silvia; Ortega-Heras, Miriam; González-Huerta, Carlos

2009-12-23

Many studies have recently been published focused on the effects of micro-oxygenation on the quality of wines, its application modes, and doses, etc. However, there are still few scientific papers on how previously micro-oxygenated wines perform during storage or barrel aging. This study focused on the evolution of the phenolic composition, especially of anthocyanins, and color, together with astringency and tannins, during micro-oxygenation before barrel aging. In addition, to evaluate whether wine evolution during aging depends on barrel type, wines were aged in four different oak barrel types. Tempranillo wines, some micro-oxygenated before malolactic fermentation and others not, were aged for 12 months in American, French, Central European, and Spanish oak, following wine evolution during that period. The study was carried out for two consecutive vintages. Results showed that all wines evolved similarly; therefore, the micro-oxygenation treatment neither accelerated nor delayed the typical changes of aging. Slightly different evolutions were detected according to the barrel wood type, whether or not the wine was micro-oxygenated. The varied evolutions must therefore be associated with the differences from each oak type (structure, grain and density, composition, etc.).

Oxygen control of breathing by an olfactory receptor activated by lactate

PubMed Central

Chang, Andy J.; Ortega, Fabian E.; Riegler, Johannes; Madison, Daniel V.; Krasnow, Mark A.

2015-01-01

Summary Animals have evolved homeostatic responses to changes in oxygen availability that act on different time scales. Although the hypoxia-inducible factor (HIF) transcriptional pathway that controls long term responses to low oxygen (hypoxia) has been established1, the pathway that mediates acute responses to hypoxia in mammals is not well understood. Here we show that the olfactory receptor Olfr78 is highly and selectively expressed in oxygen-sensitive glomus cells of the carotid body, a chemosensory organ at the carotid artery bifurcation that monitors blood oxygen and stimulates breathing within seconds when oxygen declines2. Olfr78 mutants fail to increase ventilation in hypoxia but respond normally to hypercapnia. Glomus cells are present in normal numbers and appear structurally intact, but hypoxia-induced carotid body activity is diminished. Lactate, a metabolite that rapidly accumulates in hypoxia and induces hyperventilation3–6, activates Olfr78 in heterologous expression experiments, induces calcium transients in glomus cells, and stimulates carotid sinus nerve activity through Olfr78. We propose that in addition to its role in olfaction, Olfr78 acts as a hypoxia sensor in the breathing circuit by sensing lactate produced when oxygen levels decline. PMID:26560302

Response of the ascorbate-glutathione cycle to storage temperature in carambola fruit

USDA-ARS?s Scientific Manuscript database

The generation of reactive oxygen species (ROS) is considered to be a primary event under a variety of stress conditions. It has been generally accepted that reactive oxygen produced under stress is a detrimental factor, which causes lipid peroxidation, enzyme inactivation, and oxidative damage to D...

EXAMINATION OF QUINONE TOXICITY USING YEAST SACCHAROMYCES CEREVISIAE MODEL SYSTEM. (R827352C007)

EPA Science Inventory

The toxicity of quinones is generally thought to occur by two mechanisms: the formation of covalent bonds with biological molecules by Michael addition chemistry and the catalytic reduction of oxygen to superoxide and other reactive oxygen species (ROS) (redox cycling). In an ...

Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in a Shallow, Eutrophic Estuary

EPA Science Inventory

Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...

Maximum Oxygen Uptake Determination in Insulin-Dependent Diabetes Mellitus.

ERIC Educational Resources Information Center

Fremion, Amy S.; And Others

1987-01-01

A study of 10 children with insulin-dependent diabetes mellitus performing a maximum-effort cycling test indicated blood glucose levels did not change appreciably during test, while maximal oxygen uptake was substandard for their age groups. Findings suggest patients in fair to poor metabolic control can tolerate stress testing without…

Life cycle specialization of filamentous pathogens - colonization and reproduction in plant tissues.

PubMed

Haueisen, Janine; Stukenbrock, Eva H

2016-08-01

Filamentous plant pathogens explore host tissues to obtain nutrients for growth and reproduction. Diverse strategies for tissue invasion, defense manipulation, and colonization of inter and intra-cellular spaces have evolved. Most research has focused on effector molecules, which are secreted to manipulate plant immunity and facilitate infection. Effector genes are often found to evolve rapidly in response to the antagonistic host-pathogen co-evolution but other traits are also subject to adaptive evolution during specialization to the anatomy, biochemistry and ecology of different plant hosts. Although not directly related to virulence, these traits are important components of specialization but little is known about them. We present and discuss specific life cycle traits that facilitate exploration of plant tissues and underline the importance of increasing our insight into the biology of plant pathogens. Copyright © 2016. Published by Elsevier Ltd.

Dynamic Hydrological Discharge Modelling for Fully Coupled Paleoclimate Runs of the Last Glacial Cycle

NASA Astrophysics Data System (ADS)

Riddick, Thomas; Brovkin, Victor; Hagemann, Stefan; Mikolajewicz, Uwe

2017-04-01

The continually evolving large ice sheets present in the Northern Hemisphere during the last glacial cycle caused significant changes to river pathways both through directly blocking rivers and through glacial isostatic adjustment. These river pathway changes are believed to of had a significant impact on the evolution of ocean circulation through changing the pattern of fresh water discharge into the oceans. A fully coupled ESM simulation of the last glacial cycle thus requires a hydrological discharge model that uses a set of river pathways that evolve with the earth's changing orography while being able to reproduce the known present-day river network given the present-day orography. Here we present a method for dynamically modelling hydrological discharge that meets such requirements by applying relative manual corrections to an evolving fine scale orography (accounting for the changing ice sheets and isostatic rebound) each time the river directions are recalculated. The corrected orography thus produced is then used to create a set of fine scale river pathways and these are then upscaled to a course scale. An existing present-day hydrological discharge model within the JSBACH3 land surface model is run using the course scale river pathways generated. This method will be used in fully coupled paleoclimate runs made using MPI-ESM1 as part of the PalMod project. Tests show this procedure reproduces the known present-day river network to a sufficient degree of accuracy.

Towards Predicting the Response of a Solid Tumour to Chemotherapy and Radiotherapy Treatments: Clinical Insights from a Computational Model

PubMed Central

Powathil, Gibin G.; Adamson, Douglas J. A.; Chaplain, Mark A. J.

2013-01-01

In this paper we use a hybrid multiscale mathematical model that incorporates both individual cell behaviour through the cell-cycle and the effects of the changing microenvironment through oxygen dynamics to study the multiple effects of radiation therapy. The oxygenation status of the cells is considered as one of the important prognostic markers for determining radiation therapy, as hypoxic cells are less radiosensitive. Another factor that critically affects radiation sensitivity is cell-cycle regulation. The effects of radiation therapy are included in the model using a modified linear quadratic model for the radiation damage, incorporating the effects of hypoxia and cell-cycle in determining the cell-cycle phase-specific radiosensitivity. Furthermore, after irradiation, an individual cell's cell-cycle dynamics are intrinsically modified through the activation of pathways responsible for repair mechanisms, often resulting in a delay/arrest in the cell-cycle. The model is then used to study various combinations of multiple doses of cell-cycle dependent chemotherapies and radiation therapy, as radiation may work better by the partial synchronisation of cells in the most radiosensitive phase of the cell-cycle. Moreover, using this multi-scale model, we investigate the optimum sequencing and scheduling of these multi-modality treatments, and the impact of internal and external heterogeneity on the spatio-temporal patterning of the distribution of tumour cells and their response to different treatment schedules. PMID:23874170

Metabolic and Epigenetic Interactions Regulate Vascular Phenotypic Change and Maintenance in Pulmonary Hypertension

DTIC Science & Technology

2016-10-01

Krebs cycle through the generation of alpha-ketoglutarate. However, increased oxidative stress affected oxygen consumption rates at the Complex I...machinery and respiration in PH-Fibs. The difference in endogenous respiration, (i.e., oxygen consumption ) was not statistically different compared...driven through complex I. We found a roughly17% drop in oxygen consumption in PH-Fibs versus Co-Fibs (Figure 3C), which corresponded to the down

Bistability of atmospheric oxygen and the Great Oxidation.

PubMed

Goldblatt, Colin; Lenton, Timothy M; Watson, Andrew J

2006-10-12

The history of the Earth has been characterized by a series of major transitions separated by long periods of relative stability. The largest chemical transition was the 'Great Oxidation', approximately 2.4 billion years ago, when atmospheric oxygen concentrations rose from less than 10(-5) of the present atmospheric level (PAL) to more than 0.01 PAL, and possibly to more than 0.1 PAL. This transition took place long after oxygenic photosynthesis is thought to have evolved, but the causes of this delay and of the Great Oxidation itself remain uncertain. Here we show that the origin of oxygenic photosynthesis gave rise to two simultaneously stable steady states for atmospheric oxygen. The existence of a low-oxygen (less than 10(-5) PAL) steady state explains how a reducing atmosphere persisted for at least 300 million years after the onset of oxygenic photosynthesis. The Great Oxidation can be understood as a switch to the high-oxygen (more than 5 x 10(-3) PAL) steady state. The bistability arises because ultraviolet shielding of the troposphere by ozone becomes effective once oxygen levels exceed 10(-5) PAL, causing a nonlinear increase in the lifetime of atmospheric oxygen. Our results indicate that the existence of oxygenic photosynthesis is not a sufficient condition for either an oxygen-rich atmosphere or the presence of an ozone layer, which has implications for detecting life on other planets using atmospheric analysis and for the evolution of multicellular life.

Ebullitive methane emissions from oxygenated wetland streams

USGS Publications Warehouse

Crawford, John T.; Stanley, Emily H.; Spawn, Seth A.; Finlay, Jacques C.; Striegl, Robert G.

2014-01-01

Stream and river carbon dioxide emissions are an important component of the global carbon cycle. Methane emissions from streams could also contribute to regional or global greenhouse gas cycling, but there are relatively few data regarding stream and river methane emissions. Furthermore, the available data do not typically include the ebullitive (bubble-mediated) pathway, instead focusing on emission of dissolved methane by diffusion or convection. Here, we show the importance of ebullitive methane emissions from small streams in the regional greenhouse gas balance of a lake and wetland-dominated landscape in temperate North America and identify the origin of the methane emitted from these well-oxygenated streams. Stream methane flux densities from this landscape tended to exceed those of nearby wetland diffusive fluxes as well as average global wetland ebullitive fluxes. Total stream ebullitive methane flux at the regional scale (103 Mg C yr−1; over 6400 km2) was of the same magnitude as diffusive methane flux previously documented at the same scale. Organic-rich stream sediments had the highest rates of bubble release and higher enrichment of methane in bubbles, but glacial sand sediments also exhibited high bubble emissions relative to other studied environments. Our results from a database of groundwater chemistry support the hypothesis that methane in bubbles is produced in anoxic near-stream sediment porewaters, and not in deeper, oxygenated groundwaters. Methane interacts with other key elemental cycles such as nitrogen, oxygen, and sulfur, which has implications for ecosystem changes such as drought and increased nutrient loading. Our results support the contention that streams, particularly those draining wetland landscapes of the northern hemisphere, are an important component of the global methane cycle.

Muscle Oxygen Changes following Sprint Interval Cycling Training in Elite Field Hockey Players

PubMed Central

Jones, Ben; Hamilton, David K.; Cooper, Chris E.

2015-01-01

This study examined the effects of Sprint Interval Cycling (SIT) on muscle oxygenation kinetics and performance during the 30-15 intermittent fitness test (IFT). Twenty-five women hockey players of Olympic standard were randomly selected into an experimental group (EXP) and a control group (CON). The EXP group performed six additional SIT sessions over six weeks in addition to their normal training program. To explore the potential training-induced change, EXP subjects additionally completed 5 x 30s maximal intensity cycle testing before and after training. During these tests near-infrared spectroscopy (NIRS) measured parameters; oxyhaemoglobin + oxymyoglobin (HbO2+ MbO2), tissue deoxyhaemoglobin + deoxymyoglobin (HHb+HMb), total tissue haemoglobin (tHb) and tissue oxygenation (TSI %) were taken. In the EXP group (5.34±0.14 to 5.50±0.14m.s-1) but not the CON group (pre = 5.37±0.27 to 5.39±0.30m.s-1) significant changes were seen in the 30-15IFT performance. EXP group also displayed significant post-training increases during the sprint cycling: ΔTSI (−7.59±0.91 to −12.16±2.70%); ΔHHb+HMb (35.68±6.67 to 69.44±26.48μM.cm); and ΔHbO2+ MbO2 (−74.29±13.82 to −109.36±22.61μM.cm). No significant differences were seen in ΔtHb (−45.81±15.23 to −42.93±16.24). NIRS is able to detect positive peripheral muscle oxygenation changes when used during a SIT protocol which has been shown to be an effective training modality within elite athletes. PMID:25807517

Hypotheses of cancer weakening and origin.

PubMed

Chan, John Cheung Yuen

2015-01-01

Approximately 2.7 billion years ago, cyanobacteria began producing oxygen by photosynthesis. Any free oxygen they produced was chemically captured by dissolved iron or organic matter. There was no ozone layer to protect living species against the radiation from space. Eukaryotic cells lived in water, under hypoxic environments, and metabolized glucose by fermentation. The Great Oxygenation Event (GOE) describes the point when oxygen sinks became saturated. This massive oxygenation of the Earth occurred approximately half a billion years ago. Species that evolved after the GOE are characterized by aerobic metabolism. Mammals evolved approximately a few hundred million years ago, with the ancient eukaryotic genes deeply embedded in their genome. Many genes have been exchanged by horizontal gene transfer (HGT) throughout the history of cellular evolution. Mammals have been invaded by viruses, and while viral genetic relics are embedded in mammalian junk genes, not all junk genes are genetic relics of viruses. These viral relics have been inactivated through evolution and have little impact on mammalian life. However, there is evidence to suggest that these viral genetic relics are linked to cancer. This hypothesis states that cancer develops when cell reproduction becomes defective because of the active involvement of viral genes, in a process similar to genetic engineering. Cancer cells are amalgamations of genetically modified organisms (GMOs). There are two main groups in cancer development. One group of cells arises by genetic engineering of a viral genetic relic, such as endogenous retroviruses (ERVs), which evolved after oxygenation of the atmosphere. This group is referred to here as genetically modified organisms from viral genes (GMOV). GMOVs may be inhibited by anticancer drugs. The second group arises by engineering of the genes of ancient eukaryotes, which existed prior to the oxygenation of the Earth. This second group is referred to as genetically modified organisms from ancient eukaryotic genes (GMOE). The GMOE group lives in hypoxic environments and metabolizes glucose by fermentation. GMOEs represent advanced cancer, which proliferate aggressively and are resistant to DNA damage. It has been demonstrated that as an ERV becomes more prevalent in a mammalian genome, the possibility that the mammal will develop cancer increases. The hypothesis also states that most cancers have their origins in GMOV by the incorporation of viral genes from junk genes. As the cancer progresses, further subgroups of cancer GMOs will develop. If the cancer advances even further, the GMOE could eventually develop prior to late-stage cancer. Because the genes of ancient eukaryotes have enhanced innate immunity, GMOE will eventually prevail over the weaker GMOV during cancer subgroup competition. Hence, cancer development is mainly determined by genes in the mammalian genome. An inherent weakness of cancer cells is their dependence on glucose and iron. Furthermore, they cannot tolerate physical disturbance. Ancient gene GMOs can be treated with a combination of mechanical vibration using glucose-coated magnetic nanoparticles and strengthening of the immune system. Herein, I suggest trials for verifying this hypothesis.

Hypotheses of Cancer Weakening and Origin

PubMed Central

CHAN, John Cheung Yuen

2015-01-01

Approximately 2.7 billion years ago, cyanobacteria began producing oxygen by photosynthesis. Any free oxygen they produced was chemically captured by dissolved iron or organic matter. There was no ozone layer to protect living species against the radiation from space. Eukaryotic cells lived in water, under hypoxic environments, and metabolized glucose by fermentation. The Great Oxygenation Event (GOE) describes the point when oxygen sinks became saturated. This massive oxygenation of the Earth occurred approximately half a billion years ago. Species that evolved after the GOE are characterized by aerobic metabolism. Mammals evolved approximately a few hundred million years ago, with the ancient eukaryotic genes deeply embedded in their genome. Many genes have been exchanged by horizontal gene transfer (HGT) throughout the history of cellular evolution. Mammals have been invaded by viruses, and while viral genetic relics are embedded in mammalian junk genes, not all junk genes are genetic relics of viruses. These viral relics have been inactivated through evolution and have little impact on mammalian life. However, there is evidence to suggest that these viral genetic relics are linked to cancer. This hypothesis states that cancer develops when cell reproduction becomes defective because of the active involvement of viral genes, in a process similar to genetic engineering. Cancer cells are amalgamations of genetically modified organisms (GMOs). There are two main groups in cancer development. One group of cells arises by genetic engineering of a viral genetic relic, such as endogenous retroviruses (ERVs), which evolved after oxygenation of the atmosphere. This group is referred to here as genetically modified organisms from viral genes (GMOV). GMOVs may be inhibited by anticancer drugs. The second group arises by engineering of the genes of ancient eukaryotes, which existed prior to the oxygenation of the Earth. This second group is referred to as genetically modified organisms from ancient eukaryotic genes (GMOE). The GMOE group lives in hypoxic environments and metabolizes glucose by fermentation. GMOEs represent advanced cancer, which proliferate aggressively and are resistant to DNA damage. It has been demonstrated that as an ERV becomes more prevalent in a mammalian genome, the possibility that the mammal will develop cancer increases. The hypothesis also states that most cancers have their origins in GMOV by the incorporation of viral genes from junk genes. As the cancer progresses, further subgroups of cancer GMOs will develop. If the cancer advances even further, the GMOE could eventually develop prior to late-stage cancer. Because the genes of ancient eukaryotes have enhanced innate immunity, GMOE will eventually prevail over the weaker GMOV during cancer subgroup competition. Hence, cancer development is mainly determined by genes in the mammalian genome. An inherent weakness of cancer cells is their dependence on glucose and iron. Furthermore, they cannot tolerate physical disturbance. Ancient gene GMOs can be treated with a combination of mechanical vibration using glucose-coated magnetic nanoparticles and strengthening of the immune system. Herein, I suggest trials for verifying this hypothesis. PMID:25874009

Three different [NiFe] hydrogenases confer metabolic flexibility in the obligate aerobe Mycobacterium smegmatis.

PubMed

Berney, Michael; Greening, Chris; Hards, Kiel; Collins, Desmond; Cook, Gregory M

2014-01-01

Mycobacterium smegmatis is an obligate aerobe that harbours three predicted [NiFe] hydrogenases, Hyd1 (MSMEG_2262–2263), Hyd2 (MSMEG_2720-2719) and Hyd3 (MSMEG_3931-3928). We show here that these three enzymes differ in their phylogeny, regulation and catalytic activity. Phylogenetic analysis revealed that Hyd1 groups with hydrogenases that oxidize H2 produced by metabolic processes, and Hyd2 is homologous to a novel group of putative high-affinity hydrogenases. Hyd1 and Hyd2 respond to carbon and oxygen limitation, and, in the case of Hyd1, hydrogen supplementation. Hydrogen consumption measurements confirmed that both enzymes can oxidize hydrogen. In contrast, the phylogenetic analysis and activity measurements of Hyd3 are consistent with the enzyme evolving hydrogen. Hyd3 is controlled by DosR, a regulator that responds to hypoxic conditions. The strict dependence of hydrogen oxidation of Hyd1 and Hyd2 on oxygen suggests that the enzymes are oxygen tolerant and linked to the respiratory chain. This unique combination of hydrogenases allows M. smegmatis to oxidize hydrogen at high (Hyd1) and potentially tropospheric (Hyd2) concentrations, as well as recycle reduced equivalents by evolving hydrogen (Hyd3). The distribution of these hydrogenases throughout numerous soil and marine species of actinomycetes suggests that oxic hydrogen metabolism provides metabolic flexibility in environments with changing nutrient fluxes.

New Insights into Understanding Irreversible and Reversible Lithium Storage within SiOC and SiCN Ceramics

PubMed Central

Graczyk-Zajac, Magdalena; Reinold, Lukas Mirko; Kaspar, Jan; Sasikumar, Pradeep Vallachira Warriam; Soraru, Gian-Domenico; Riedel, Ralf

2015-01-01

Within this work we define structural properties of the silicon carbonitride (SiCN) and silicon oxycarbide (SiOC) ceramics which determine the reversible and irreversible lithium storage capacities, long cycling stability and define the major differences in the lithium storage in SiCN and SiOC. For both ceramics, we correlate the first cycle lithiation or delithiation capacity and cycling stability with the amount of SiCN/SiOC matrix or free carbon phase, respectively. The first cycle lithiation and delithiation capacities of SiOC materials do not depend on the amount of free carbon, while for SiCN the capacity increases with the amount of carbon to reach a threshold value at ~50% of carbon phase. Replacing oxygen with nitrogen renders the mixed bond Si-tetrahedra unable to sequester lithium. Lithium is more attracted by oxygen in the SiOC network due to the more ionic character of Si-O bonds. This brings about very high initial lithiation capacities, even at low carbon content. If oxygen is replaced by nitrogen, the ceramic network becomes less attractive for lithium ions due to the more covalent character of Si-N bonds and lower electron density on the nitrogen atom. This explains the significant difference in electrochemical behavior which is observed for carbon-poor SiCN and SiOC materials. PMID:28347008

A highly stable (SnOx-Sn)@few layered graphene composite anode of sodium-ion batteries synthesized by oxygen plasma assisted milling

NASA Astrophysics Data System (ADS)

Cheng, Deliang; Liu, Jiangwen; Li, Xiang; Hu, Renzong; Zeng, Meiqing; Yang, Lichun; Zhu, Min

2017-05-01

The (SnOx-Sn)@few layered graphene ((SnOx-Sn)@FLG) composite has been synthesized by oxygen plasma-assisted milling. Owing to the synergistic effect of rapid plasma heating and ball mill grinding, SnOx (1 ≤ x ≤ 2) nanoparticles generated from the reaction of Sn with oxygen are tightly wrapped by FLG nanosheets which are simultaneously exfoliated from expanded graphite, forming secondary micro granules. Inside the granules, the small size of the SnOx nanoparticles enables the fast kinetics for Na+ transfer. The in-situ formed FLG and residual Sn nanoparticles improve the electrical conductivity of the composite, meanwhile alleviate the aggregation of SnOx nanoparticles and relieve the volume change during the cycling, which is beneficial for the cyclic stability for the Na+ storage. As an anode material for sodium-ion batteries, the (SnOx-Sn)@FLG composite exhibits a high reversible capacity of 448 mAh g-1 at a current density of 100 mA g-1 in the first cycle, with 82.6% capacity retention after 250 cycles. Even when the current density increases to 1000 mA g-1, this composite retains 316.5 mAh g-1 after 250 cycles. With superior Na+ storage stability, the (SnOx-Sn)@FLG composite can be a promising anode material for high performance sodium-ion batteries.

The effect of functional electrical stimulation cycling on late functional improvement in patients with chronic incomplete spinal cord injury.

PubMed

Yaşar, E; Yılmaz, B; Göktepe, S; Kesikburun, S

2015-12-01

Prospective single-arm study. To investigate the effect of functional electrical stimulation (FES) cycling on late functional recovery, spasticity, gait parameters and oxygen consumption during walking in patients with chronic incomplete spinal cord injury (SCI). Turkish Armed Forces Rehabilitation Center, Ankara, Turkey. Ten patients with chronic (duration of more than 2 years) incomplete SCI who could ambulate at least 10 m independently or with the assistance of a cane or walker, but no hip-knee-ankle-foot orthosis. The subjects underwent 1-h FES cycling sessions three times a week for 16 weeks. Outcome measures including the total motor score, the Functional Independence Measure (FIM) score, the Modified Ashworth Scale for knee spasticity, temporal spatial gait parameters and oxygen consumption rate during walking were assessed at baseline, 3 and 6 months after the baseline. There were statistically significant improvements in total motor scores, the FIM scores and spasticity level at the 6-month follow-up (P<0.01). The changes in gait parameters reached no significant level (P>0.05). Oxygen consumption rate of the patients showed significant reduction at only 6 months compared with baseline (P<0.01). The results suggest that FES cycling may provide some functional improvements in the late period of SCI. The study was supported by The Scientific and Technological Research Council of Turkey (TUBITAK).

The oxygen isotopes

NASA Astrophysics Data System (ADS)

Alex Brown, B.

The properties of the oxygen isotopes provide diverse examples of progress made in experiments and theory. This chain of isotopes has been studied from beyond the proton drip line in 12O to beyond the neutron drip line in 25,26O. This short survey starts with the microscopic G matrix approach for 18O of Kuo and Brown in the 1960's and shows how theory has evolved. The nuclear structure around the doubly-magic nucleus 24O is particularly simple in terms of the nuclear shell model. The nuclear structure around the doubly-magic nucleus 16O exhibits the coexistence of single-particle and collective structure.

History of chemical oxygen-iodine laser (COIL) development in the USA

NASA Astrophysics Data System (ADS)

Truesdell, Keith A.; Helms, Charles A.; Hager, Gordon D.

1994-09-01

This is an overview of the development of Chemical Oxygen-Iodine Laser (COIL) technology in the United States. Key technical developments will be reviewed, beginning in 1960 and culminating in 1977 with the first COIL lasing demonstration at the Air Force Weapons Laboratory (now the Phillips Laboratory). The discussion will then turn to subsonic laser development, supersonic lasing demonstration and efficiency improvements, and finishing with a brief discussion of some spin off COIL technologies. Particular emphasis will be placed on how the O2 (1(Delta) ) generator and O2-I2 mixing nozzle technologies evolved.

History of chemical oxygen-iodine laser (COIL) development in the USA

NASA Astrophysics Data System (ADS)

Truesdell, Keith A.; Helms, Charles A.; Hager, Gordon D.

1995-03-01

This is an overview of the development of Chemical Oxygen-Iodine Laser (COIL) technology in the United States. Key technical developments will be reviewed, beginning in 1960 and culminating in 1977 with the first COIL lasing demonstration at the Air Force Weapons Laboratory (now the Phillips Laboratory). The discussion will then turn to subsonic laser development, supersonic lasing demonstration and efficiency improvements, and finishing with a brief discussion of some spin off COIL technologies. Particular emphasis will be placed on how the O2 (1(Delta) ) generator and O2-I2 mixing nozzle technologies evolved.

Molecular dynamics studies of pathways of water movement in cyanobacterial photosystem II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabdulkhakov, A. G., E-mail: azat@vega.protres.ru; Kljashtorny, V. G.; Dontsova, M. V.

2015-01-15

Photosystem II (PSII) catalyzes the light-induced generation of oxygen from water. The oxygen-evolving complex is buried deep in the protein on the lumenal side of PSII, and water molecules need to pass through protein subunits to reach the active site—the manganese cluster. Previous studies on the elucidation of water channels in PSII were based on an analysis of the cavities in the static PSII structure determined by X-ray diffraction. In the present study, we perform molecular dynamics simulations of the water movement in the transport system of PSII.

Modern and ancient geochemical constraints on Proterozoic atmosphere-ocean redox evolution

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Horner, T. J.; Wankel, S. D.; Lu, Z.; Lyons, T.; Nielsen, S.

2017-12-01

A detailed understanding of the spatiotemporal oxygenation of Earth's atmosphere-ocean system through the Precambrian has important implications for the environments capable of sustaining early eukaryotic life and the evolving oxidant budget of subducted sediments. Proxy records suggest an anoxic Fe-rich deep ocean through much of the Precambrian and atmospheric and surface-ocean oxygenation that started in earnest at the Paleoproterozoic Great Oxidation Event (GOE). The marine photic zone represented the initial site of oxygen production and accumulation via cyanobacteria, yet our understanding of surface-ocean oxygen contents and the extent and timing of oxygen propagation and exchange between the atmosphere and deeper ocean are limited. Here, we present an updated perspective of the constraints on atmospheric, surface-ocean, and deep-ocean oxygen contents starting at the GOE. Our research uses the iodine content of Proterozoic carbonates as a tracer of dissolved iodate in the shallow ocean, a redox-sensitive species quantitatively reduced in modern oxygen minimum zones. We supplement our understanding of the ancient record with novel experiments examining the rates of iodate production from oxygenated marine environments based on seawater incubations. Combining new data from iodine with published shallow marine (Ce anomaly, N isotopes) and atmospheric redox proxies, we provide an integrated view of the vertical redox structure of the atmosphere and ocean across the Proterozoic.

The Secretion of Oxygen into the Swim-bladder of Fish

PubMed Central

Wittenberg, Jonathan B.; Wittenberg, Beatrice A.

1961-01-01

Toadfish, Opsanus tau, L., were maintained in sea water equilibrated with gas mixtures containing a fixed proportion of oxygen and varying proportions of carbon monoxide. The swim-bladder was emptied by puncture, and, after an interval of 24 or 48 hours, the newly secreted gases were withdrawn and analyzed. Both carbon monoxide and oxygen are accumulated in the swim-bladder at tensions greater than ambient. The ratio of concentrations, carbon monoxide (secreted): carbon monoxide (administered) bears a constant relation to the ratio, oxygen (secreted): oxygen (administered). The value of the partition coefficient describing this relation is (α = 5.44). The two gases are considered to compete for a common intracellular carrier mediating their active transport. The suggestion is advanced that the intracellular oxygen carrier is a hemoglobin. Comparison of the proportions of carboxy- and oxyhemoglobin in the blood with the composition of the secreted gas proves that the secreted gases are not evolved directly from combination with blood hemoglobin. The suggestion is advanced that cellular oxygen secretion occurs in the rete mirabile: the rete may build up large oxygen tensions in the gas gland capillaries. It is suggested that the gas gland acts as a valve impeding back diffusion of gases from the swim-bladder. PMID:13786093

Inherent N,O-containing carbon frameworks as electrode materials for high-performance supercapacitors.

PubMed

Hu, Fangyuan; Wang, Jinyan; Hu, Shui; Li, Linfei; Wang, Gang; Qiu, Jieshan; Jian, Xigao

2016-09-15

N,O-Containing micropore-dominated materials have been developed successfully via temperature-dependent cross-linking of 4,4'-(dioxo-diphenyl-2,3,6,7-tetraazaanthracenediyl)dibenzonitrile (DPDN) monomers. By employing a molecular engineering strategy, we have designed and synthesized a series of porous heteroatom-containing carbon frameworks (PHCFs), in which nitrogen and oxygen heteroatoms are distributed homogeneously throughout the whole framework at the atomic level, which can ensure the stability of its electrical properties. The as-made PHCFs@550 exhibits a high specific capacitance of 378 F g -1 , with an excellent long cycling life, including excellent cycling stability (capacitance retention of ca. 120% over 20 000 cycles). Moreover, the successful preparation of PHCFs provides new insights for the fabrication of nitrogen and oxygen-containing electrode materials from readily available components via a facile route.

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2017-09-24

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaffer, David W.; Xie, Yan; Szalda, David J.

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

The impact of rapid evolution on population dynamics in the wild: experimental test of eco-evolutionary dynamics.

PubMed

Turcotte, Martin M; Reznick, David N; Hare, J Daniel

2011-11-01

Rapid evolution challenges the assumption that evolution is too slow to impact short-term ecological dynamics. This insight motivates the study of 'Eco-Evolutionary Dynamics' or how evolution and ecological processes reciprocally interact on short time scales. We tested how rapid evolution impacts concurrent population dynamics using an aphid (Myzus persicae) and an undomesticated host (Hirschfeldia incana) in replicated wild populations. We manipulated evolvability by creating non-evolving (single clone) and potentially evolving (two-clone) aphid populations that contained genetic variation in intrinsic growth rate. We observed significant evolution in two-clone populations whether or not they were exposed to predators and competitors. Evolving populations grew up to 42% faster and attained up to 67% higher density, compared with non-evolving control populations but only in treatments exposed to competitors and predators. Increased density also correlates with relative fitness of competing clones suggesting a full eco-evolutionary dynamic cycle defined as reciprocal interactions between evolution and density. © 2011 Blackwell Publishing Ltd/CNRS.

Managing laboratory automation

PubMed Central

Saboe, Thomas J.

1995-01-01

This paper discusses the process of managing automated systems through their life cycles within the quality-control (QC) laboratory environment. The focus is on the process of directing and managing the evolving automation of a laboratory; system examples are given. The author shows how both task and data systems have evolved, and how they interrelate. A BIG picture, or continuum view, is presented and some of the reasons for success or failure of the various examples cited are explored. Finally, some comments on future automation need are discussed. PMID:18925018

Managing laboratory automation.

PubMed

Saboe, T J

1995-01-01

This paper discusses the process of managing automated systems through their life cycles within the quality-control (QC) laboratory environment. The focus is on the process of directing and managing the evolving automation of a laboratory; system examples are given. The author shows how both task and data systems have evolved, and how they interrelate. A BIG picture, or continuum view, is presented and some of the reasons for success or failure of the various examples cited are explored. Finally, some comments on future automation need are discussed.

Net community production at Ocean Station Papa observed with nitrate and oxygen sensors on profiling floats

NASA Astrophysics Data System (ADS)

Plant, Joshua N.; Johnson, Kenneth S.; Sakamoto, Carole M.; Jannasch, Hans W.; Coletti, Luke J.; Riser, Stephen C.; Swift, Dana D.

2016-06-01

Six profiling floats equipped with nitrate and oxygen sensors were deployed at Ocean Station P in the Gulf of Alaska. The resulting six calendar years and 10 float years of nitrate and oxygen data were used to determine an average annual cycle for net community production (NCP) in the top 35 m of the water column. NCP became positive in February as soon as the mixing activity in the surface layer began to weaken, but nearly 3 months before the traditionally defined mixed layer began to shoal from its winter time maximum. NCP displayed two maxima, one toward the end of May and another in August with a summertime minimum in June corresponding to the historical peak in mesozooplankton biomass. The average annual NCP was determined to be 1.5 ± 0.6 mol C m-2 yr-1 using nitrate and 1.5 ± 0.7 mol C m-2 yr-1 using oxygen. The results from oxygen data proved to be quite sensitive to the gas exchange model used as well as the accuracy of the oxygen measurement. Gas exchange models optimized for carbon dioxide flux generally ignore transport due to gas exchange through the injection of bubbles, and these models yield NCP values that are two to three time higher than the nitrate-based estimates. If nitrate and oxygen NCP rates are assumed to be related by the Redfield model, we show that the oxygen gas exchange model can be optimized by tuning the exchange terms to reproduce the nitrate NCP annual cycle.

Oxygen isotopes of phosphatic compounds - Application for marine particulate matter, sediments and soils

USGS Publications Warehouse

McLaughlin, K.; Paytan, A.; Kendall, C.; Silva, S.

2006-01-01

The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (??18Op) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO 43-). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H218O (spiked) and unspiked acid and then converted the samples to silver phosphate for ??18Op analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50??C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the ??18O p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for ??18O p to demonstrate the utility of this approach for understanding sources and cycling of P. ?? 2005 Elsevier B.V. All rights reserved.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

PubMed

Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

2018-03-21

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

Large fluctuations of dissolved oxygen in the Indian and Pacific oceans during Dansgaard-Oeschger oscillations caused by variations of North Atlantic Deep Water subduction

USGS Publications Warehouse

Schmittner, A.; Galbraith, E.D.; Hostetler, S.W.; Pedersen, Thomas F.; Zhang, R.

2007-01-01

Paleoclimate records from glacial Indian and Pacific oceans sediments document millennial-scale fluctuations of subsurface dissolved oxygen levels and denitrification coherent with North Atlantic temperature oscillations. Yet the mechanism of this teleconnection between the remote ocean basins remains elusive. Here we present model simulations of the oxygen and nitrogen cycles that explain how changes in deepwater subduction in the North Atlantic can cause large and synchronous variations of oxygen minimum zones, throughout the Northern Hemisphere of the Indian and Pacific oceans, consistent with the paleoclimate records. Cold periods in the North Atlantic are associated with reduced nutrient delivery to the upper Indo-Pacific oceans, thereby decreasing productivity. Reduced export production diminishes subsurface respiration of organic matter leading to higher oxygen concentrations and less denitrification. This effect of reduced oxygen consumption dominates at low latitudes. At high latitudes in the Southern Ocean and North Pacific, increased mixed layer depths and steepening of isopycnals improve ocean ventilation and oxygen supply to the subsurface. Atmospheric teleconnections through changes in wind-driven ocean circulation modify this basin-scale pattern regionally. These results suggest that changes in the Atlantic Ocean circulation, similar to those projected by climate models to possibly occur in the centuries to come because of anthropogenic climate warming, can have large effects on marine ecosystems and biogeochemical cycles even in remote areas. Copyright 2007 by the American Geophysical Union.

Effect of surface oxygen vacancy sites on ethanol synthesis from acetic acid hydrogenation on a defective In2O3(110) surface.

PubMed

Lyu, Huisheng; Liu, Jiatao; Chen, Yifei; Li, Guiming; Jiang, Haoxi; Zhang, Minhua

2018-03-07

Developing a new type of low-cost and high-efficiency non-noble metal catalyst is beneficial for industrially massive synthesis of alcohols from carboxylic acids which can be obtained from renewable biomass. In this work, the effect of active oxygen vacancies on ethanol synthesis from acetic acid hydrogenation over defective In 2 O 3 (110) surfaces has been studied using periodic density functional theory (DFT) calculations. The relative stabilities of six surface oxygen vacancies from O v1 to O v6 on the In 2 O 3 (110) surface were compared. D1 and D4 surfaces with respective O v1 and O v4 oxygen vacancies were chosen to map out the reaction paths from acetic acid to ethanol. A reaction cycle mechanism between the perfect and defective states of the In 2 O 3 surface was found to catalyze the formation of ethanol from acetic acid hydrogenation. By H 2 reduction the oxygen vacancies on the In 2 O 3 surface play key roles in promoting CH 3 COO* hydrogenation and C-O bond breaking in acetic acid hydrogenation. The acetic acid, in turn, benefits the creation of oxygen vacancies, while the C-O bond breaking of acetic acid refills the oxygen vacancy and, thereby, sustains the catalytic cycle. The In 2 O 3 based catalysts were shown to be advantageous over traditional noble metal catalysts in this paper by theoretical analysis.

Sensors, transmitters, and targets in mitochondrial oxygen shortage-a hypoxia-inducible factor relay story.

PubMed

Dehne, Nathalie; Brüne, Bernhard

2014-01-10

Cells sense and respond to a shortage of oxygen by activating the hypoxia-inducible transcription factors HIF-1 and HIF-2 and evoking adaptive responses. Mitochondria are at the center of a hypoxia sensing and responding relay system. Under normoxia, reactive oxygen species (ROS) and nitric oxide (NO) are HIF activators. As their individual flux rates determine their diffusion-controlled interaction, predictions how these radicals affect HIF appear context-dependent. Considering that the oxygen requirement for NO formation limits its role in activating HIF to conditions of ambient oxygen tension. Given the central role of mitochondrial complex IV as a NO target, especially under hypoxia, allows inhibition of mitochondrial respiration by NO to spare oxygen thus, raising the threshold for HIF activation. HIF targets seem to configure a feedback-signaling circuit aimed at gradually adjusting mitochondrial function. In hypoxic cancer cells, mitochondria redirect Krebs cycle intermediates to preserve their biosynthetic ability. Persistent HIF activation lowers the entry of electron-delivering compounds into mitochondria to reduce Krebs cycle fueling and β-oxidation, attenuates the expression of electron transport chain components, limits mitochondria biosynthesis, and provokes their removal by autophagy. Mitochondria can be placed central in a hypoxia sensing-hypoxia responding circuit. We need to determine to which extent and how mitochondria contribute to sense hypoxia, explore whether modulating their oxygen-consuming capacity redirects hypoxic responses in in vivo relevant disease conditions, and elucidate how the multiple HIF targets in mitochondria shape conditions of acute versus chronic hypoxia.

FeO2 and FeOOH under deep lower-mantle conditions and Earth's oxygen-hydrogen cycles.

PubMed

Hu, Qingyang; Kim, Duck Young; Yang, Wenge; Yang, Liuxiang; Meng, Yue; Zhang, Li; Mao, Ho-Kwang

2016-06-09

The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.

Temporal and Spatial Variability of the Martian Hot Oxygen Corona

NASA Astrophysics Data System (ADS)

Deighan, J.; Jain, S.; Chaffin, M.; Chaufray, J. Y.; Schneider, N. M.; Clarke, J. T.; Mayyasi, M.; Lillis, R. J.; Eparvier, F. G.; Thiemann, E.; Chamberlin, P. C.

2017-12-01

The dominant loss mechanism of oxygen from Mars to space in the current epoch is thought to be photochemical escape of hot oxygen produced by dissociative recombination of O2+. This ion is ultimately sourced from CO2+, which is the primary product of photoionization. The escaping hot oxygen population is accompanied by a gravitationally bound hot oxygen corona produced by the same mechanism. The MAVEN spacecraft has been at Mars since November 2014, with multiple seasons suitable for the IUVS instrument to observe the dayside hot oxygen corona via fluorescence of the O I 130.4 nm triplet. This provides the opportunity to examine temporal variations associated with changes in the photoionizing solar EUV radiation which produces CO2+ and O2+ ions. We present results based on two seasons: LS = 270 in Mars Year 32 during the maximum of Solar Cycle 24 and LS = 210 in Mars Year 33 late in the declining phase of the same Solar Cycle. The data in both seasons contain multiple solar rotations. We compare the oxygen corona density to the EUV solar flux measured by MAVEN/EUVM and ionization frequencies calculated therefrom. The peak brightness of ionospheric CO2+ UVD emission from IUVS limb scans is also used as a direct indicator of the photoionization frequency. As expected, the result is a strong correlation between solar EUV input, observed ionization frequency, and the density of the hot oxygen corona. In addition, a new observation strategy was employed during the MY 33 season to view the Martian corona near the sub-solar point with anti-parallel lines of sight from opposing hemispheres. These observations reveal a significant hemispherical asymmetry in brightness, providing a constraint on the large scale spatial variability of the dayside oxygen corona.

High Oxygen Delivery to Preserve Exercise Capacity in Patients with Idiopathic Pulmonary Fibrosis Treated with Nintedanib. Methodology of the HOPE-IPF Study.

PubMed

Ryerson, Christopher J; Camp, Pat G; Eves, Neil D; Schaeffer, Michele; Syed, Nafeez; Dhillon, Satvir; Jensen, Dennis; Maltais, Francois; O'Donnell, Denis E; Raghavan, Natya; Roman, Michael; Stickland, Michael K; Assayag, Deborah; Bourbeau, Jean; Dion, Genevieve; Fell, Charlene D; Hambly, Nathan; Johannson, Kerri A; Kalluri, Meena; Khalil, Nasreen; Kolb, Martin; Manganas, Helene; Morán-Mendoza, Onofre; Provencher, Steve; Ramesh, Warren; Rolf, J Douglass; Wilcox, Pearce G; Guenette, Jordan A

2016-09-01

Pulmonary rehabilitation improves dyspnea and exercise capacity in idiopathic pulmonary fibrosis (IPF); however, it is unknown whether breathing high amounts of oxygen during exercise training leads to further benefits. Herein, we describe the design of the High Oxygen Delivery to Preserve Exercise Capacity in IPF Patients Treated with Nintedanib study (the HOPE-IPF study). The primary objective of this study is to determine the physiological and perceptual impact of breathing high levels of oxygen during exercise training in patients with IPF who are receiving antifibrotic therapy. HOPE-IPF is a two-arm double-blind multicenter randomized placebo-controlled trial of 88 patients with IPF treated with nintedanib. Patients will undergo 8 weeks of three times weekly aerobic cycle exercise training, breathing a hyperoxic gas mixture with a constant fraction of 60% inhaled oxygen, or breathing up to 40% oxygen as required to maintain an oxygen saturation level of at least 88%. End points will be assessed at baseline, postintervention (Week 8), and follow-up (Week 26). The primary analysis will compare the between-group baseline with post-training change in endurance time during constant work rate cycle exercise tests. Additional analyses will evaluate the impact of training with high oxygen delivery on 6-minute walk distance, dyspnea, physical activity, and quality of life. The HOPE-IPF study will lead to a comprehensive understanding of IPF exercise physiology, with the potential to change clinical practice by indicating the need for increased delivery of supplemental oxygen during pulmonary rehabilitation in patients with IPF. Clinical trial registered with www.clinicaltrials.gov (NCT02551068).

Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

NASA Astrophysics Data System (ADS)

Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

2017-12-01

The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on Geochemistry (2nd. Ed.), H. D. Holland, K. K. Turekian, Eds. (Elsevier, Oxford, 2014), 239-249. [2] S. J. Daines, B. J. W. Mills, and T. M. Lenton, Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon, Nat. Commun. 8 (2017): 14379.

Cell cycle progression is an essential regulatory component of phospholipid metabolism and membrane homeostasis

PubMed Central

Sanchez-Alvarez, Miguel; Zhang, Qifeng; Finger, Fabian; Wakelam, Michael J. O.; Bakal, Chris

2015-01-01

We show that phospholipid anabolism does not occur uniformly during the metazoan cell cycle. Transition to S-phase is required for optimal mobilization of lipid precursors, synthesis of specific phospholipid species and endoplasmic reticulum (ER) homeostasis. Average changes observed in whole-cell phospholipid composition, and total ER lipid content, upon stimulation of cell growth can be explained by the cell cycle distribution of the population. TORC1 promotes phospholipid anabolism by slowing S/G2 progression. The cell cycle stage-specific nature of lipid biogenesis is dependent on p53. We propose that coupling lipid metabolism to cell cycle progression is a means by which cells have evolved to coordinate proliferation with cell and organelle growth. PMID:26333836

Cell cycle progression is an essential regulatory component of phospholipid metabolism and membrane homeostasis.

PubMed

Sanchez-Alvarez, Miguel; Zhang, Qifeng; Finger, Fabian; Wakelam, Michael J O; Bakal, Chris

2015-09-01

We show that phospholipid anabolism does not occur uniformly during the metazoan cell cycle. Transition to S-phase is required for optimal mobilization of lipid precursors, synthesis of specific phospholipid species and endoplasmic reticulum (ER) homeostasis. Average changes observed in whole-cell phospholipid composition, and total ER lipid content, upon stimulation of cell growth can be explained by the cell cycle distribution of the population. TORC1 promotes phospholipid anabolism by slowing S/G2 progression. The cell cycle stage-specific nature of lipid biogenesis is dependent on p53. We propose that coupling lipid metabolism to cell cycle progression is a means by which cells have evolved to coordinate proliferation with cell and organelle growth. © 2015 The Authors.

Nitrogen oxides from burning forest fuels examined by thermogravimetry and evolved gas analysis

Treesearch

H.B. Clements; Charles K. McMahon

1980-01-01

Abstract. Twelve forest fuels that varied widely in nitrogen content were burned in a thermogravimetric system, and nitrogen oxide production was analyzed by chemiluminescence. The effects of fuel nitrogen concentration, available oxygen, flow rate, and heating rate on nitrogen oxide production were examined.Results show that fuel nitrogen is an...

Improving the efficiency of dissolved oxygen control using an on-line control system based on a genetic algorithm evolving FWNN software sensor.

PubMed

Ruan, Jujun; Zhang, Chao; Li, Ya; Li, Peiyi; Yang, Zaizhi; Chen, Xiaohong; Huang, Mingzhi; Zhang, Tao

2017-02-01

This work proposes an on-line hybrid intelligent control system based on a genetic algorithm (GA) evolving fuzzy wavelet neural network software sensor to control dissolved oxygen (DO) in an anaerobic/anoxic/oxic process for treating papermaking wastewater. With the self-learning and memory abilities of neural network, handling the uncertainty capacity of fuzzy logic, analyzing local detail superiority of wavelet transform and global search of GA, this proposed control system can extract the dynamic behavior and complex interrelationships between various operation variables. The results indicate that the reasonable forecasting and control performances were achieved with optimal DO, and the effluent quality was stable at and below the desired values in real time. Our proposed hybrid approach proved to be a robust and effective DO control tool, attaining not only adequate effluent quality but also minimizing the demand for energy, and is easily integrated into a global monitoring system for purposes of cost management. Copyright © 2016 Elsevier Ltd. All rights reserved.

The evolution of glutathione metabolism in phototrophic microorganisms

NASA Technical Reports Server (NTRS)

Fahey, Robert C.; Buschbacher, Ralph M.; Newton, Gerald L.

1988-01-01

The low molecular weight thiol composition of a variety of phototropic microorganisms is examined in order to ascertain how evolution of glutathione (GSH) production is related to the evolution of oxygenic photosynthesis. Cells were extracted in the presence of monobromobimane (mBBr) to convert thiols (RSH) to fluorescent derivatives (RSmB) which were analyzed by high performance liquid chromatography (HPLC). Significant levels of GSH were not found in green sulfur bacteria. Substantial levels were present in purple bacteria, cyanobacteria, and eukaryotic algae. Other thiols measured included cysteine, gamma-glutamylcysteine, thiosulfate, coenzyme A, and sulfide. Many of the organisms also exhibited a marked ability to reduce mBBr to syn-(methyl,methyl)bimane, an ability which was quenched by treatment with 2-pyridyl disulfide or 5,5 prime-bisdithio - (2-nitrobenzoic acid) prior to reaction with mBBr. These observations indicate the presence of a reducing system capable of electron transfer to mBBr and reduction of reactive disulfides. The distribution of GSH in phototropic eubacteria indicates that GSH synthesis evolved at or around the time that oxygenic photosynthesis evolved.

Renal Carcinogenesis, Tumor Heterogeneity, and Reactive Oxygen Species: Tactics Evolved

PubMed Central

Shanmugasundaram, Karthigayan

2016-01-01

Abstract Significance: The number of kidney cancers is growing 3–5% each year due to unknown etiologies. Intra- and inter-tumor mediators increase oxidative stress and drive tumor heterogeneity. Recent Advances: Technology advancement in state-of-the-art instrumentation and methodologies allows researchers to detect and characterize global landscaping modifications in genes, proteins, and pathophysiology patterns at the single-cell level. Critical Issues: We postulate that the sources of reactive oxygen species (ROS) and their activation within subcellular compartments will change over a timeline of tumor evolvement and contribute to tumor heterogeneity. Therefore, the complexity of intracellular changes within a tumor and ROS-induced tumor heterogeneity coupled to the advancement of detecting these events globally are limited at the level of data collection, organization, and interpretation using software algorithms and bioinformatics. Future Directions: Integrative and collaborative research, combining the power of numbers with careful experimental design, protocol development, and data interpretation, will translate cancer biology and therapeutics to a heightened level or leave the abundant raw data as stagnant and underutilized. Antioxid. Redox Signal. 25, 685–701. PMID:27287984

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

PubMed

Jin, Zhaoyu; Li, Panpan; Xiao, Dan

2017-02-08

Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Knee Joint Extension on Submaximal Oxygen Consumption and Anaerobic Power in Cyclists

DTIC Science & Technology

1991-06-05

Cycling (pp. 91-122). Champaign, IL: Human Kinetics Books. Cavanagh, P.R. & Kram, R. (1985). Mechanical and muscular factors affecting the efficiency...M.L. (1986). Flexibility standards of the U.S. cycling team. In E.R. Burke (Ed.). Science of Cycling (pp. 47-68). Champaign, IL: Human Kinetics Books...height and pedaling cadence on power output and efficiency. In E.R. Burke (Ed.). Science of Cycling (pp. 69-907). Champaign, IL: Human Kinetics Books

The long-term carbon cycle, fossil fuels and atmospheric composition.

PubMed

Berner, Robert A

2003-11-20

The long-term carbon cycle operates over millions of years and involves the exchange of carbon between rocks and the Earth's surface. There are many complex feedback pathways between carbon burial, nutrient cycling, atmospheric carbon dioxide and oxygen, and climate. New calculations of carbon fluxes during the Phanerozoic eon (the past 550 million years) illustrate how the long-term carbon cycle has affected the burial of organic matter and fossil-fuel formation, as well as the evolution of atmospheric composition.

Conceptual design of a lunar oxygen pilot plant Lunar Base Systems Study (LBSS) task 4.2

NASA Technical Reports Server (NTRS)

1988-01-01

The primary objective was to develop conceptual designs of two pilot plants to produce oxygen from lunar materials. A lunar pilot plant will be used to generate engineering data necessary to support an optimum design of a larger scale production plant. Lunar oxygen would be of primary value as spacecraft propellant oxidizer. In addition, lunar oxygen would be useful for servicing nonregenerative fuel cell power systems, providing requirements for life support, and to make up oxygen losses from leakage and airlock cycling. Thirteen different lunar oxygen production methods are described. Hydrogen reduction of ilmenite and extraction of solar-wind hydrogen from bulk lunar soil were selected for conceptual design studies. Trades and sensitivity analyses were performed with these models.

P53 Suppression of Homologous Recombination and Tumorigenesis

DTIC Science & Technology

2013-07-01

cell cycle [22] and is known to have an important role in responding to oxygen concentration, particularly hypoxia (,1% O2) [23] or hyperoxia (95% O2...appropriate oxygen tension for in vitro culture? Mol Hum Reprod 12: 653. 2. Csete M (2005) Oxygen in the cultivation of stem cells . Ann N Y Acad Sci 1049: 1...culture that were derived from somatic mesenchymal cells that display a reasonable level of clonality. Yet, given the highly proliferative nature

Decreased muscle oxygenation and increased arterial blood flow in the non-exercising limb during leg exercise.

PubMed

Shiroishi, Kiyoshi; Kime, Ryotaro; Osada, Takuya; Murase, Norio; Shimomura, Kousuke; Katsumura, Toshihito

2010-01-01

We evaluated arterial blood flow, muscle tissue oxygenation and muscle metabolism in the non-exercising limb during leg cycling exercise. Ten healthy male volunteers performed a graded leg cycling exercise at 0, 40, 80, 120 and 160 watts (W) for 5 min each. Tissue oxygenation index (TOI) of the non-exercising left forearm muscle was measured using a near-infrared spatially resolved spectroscopy (NIR(SRS)), and non-exercising forearm blood flow ((NONEX)FBF) in the brachial artery was also evaluated by a Doppler ultrasound system. We also determined O(2) consumption of the non-exercising forearm muscle (NONEXV(O)(2mus)) by the rate of decrease in O(2)Hb during arterial occlusion at each work rate. TOI was significantly decreased at 160 W (p < 0.01) compared to the baseline. The (NONEX)V(O)(2mus) at each work rate was not significantly increased. In contrast, (NONEX)FBF was significantly increased at 120 W (p < 0.05) and 160 W (p < 0.01) compared to the baseline. These results suggest that the O(2) supply to the non-exercising muscle may be reduced, even though (NONEX)FBF increases at high work rates during leg cycling exercise.

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

DOE PAGES

Gent, William E.; Lim, Kipil; Liang, Yufeng; ...

2017-12-01

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gent, William E.; Lim, Kipil; Liang, Yufeng

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by >more » 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.« less

Reconciliation of late Quaternary sea levels derived from coral terraces at Huon Peninsula with deep sea oxygen isotope records

NASA Astrophysics Data System (ADS)

Chappell, John; Omura, Akio; Esat, Tezer; McCulloch, Malcolm; Pandolfi, John; Ota, Yoko; Pillans, Brad

1996-06-01

A major discrepancy between the Late Quaternary sea level changes derived from raised coral reef terraces at the Huon Peninsula in Papua New Guinea and from oxygen isotopes in deep sea cores is resolved. The two methods agree closely from 120 ka to 80 ka and from 20 ka to 0 ka (ka = 1000 yr before present), but between 70 and 30 ka the isotopic sea levels are 20-40 m lower than the Huon Peninsula sea levels derived in earlier studies. New, high precision U-series age measurements and revised stratigraphic data for Huon Peninsula terraces aged between 30 and 70 ka now give similar sea levels to those based on deep sea oxygen isotope data planktonic and benthic δ 18O data. Using the sea level and deep sea isotopic data, oxygen isotope ratios are calculated for the northern continental ice sheets through the last glacial cycle and are consistent with results from Greenland ice cores. The record of ice volume changes through the last glacial cycle now appears to be reasonably complete.

JavaGenes and Condor: Cycle-Scavenging Genetic Algorithms

NASA Technical Reports Server (NTRS)

Globus, Al; Langhirt, Eric; Livny, Miron; Ramamurthy, Ravishankar; Soloman, Marvin; Traugott, Steve

2000-01-01

A genetic algorithm code, JavaGenes, was written in Java and used to evolve pharmaceutical drug molecules and digital circuits. JavaGenes was run under the Condor cycle-scavenging batch system managing 100-170 desktop SGI workstations. Genetic algorithms mimic biological evolution by evolving solutions to problems using crossover and mutation. While most genetic algorithms evolve strings or trees, JavaGenes evolves graphs representing (currently) molecules and circuits. Java was chosen as the implementation language because the genetic algorithm requires random splitting and recombining of graphs, a complex data structure manipulation with ample opportunities for memory leaks, loose pointers, out-of-bound indices, and other hard to find bugs. Java garbage-collection memory management, lack of pointer arithmetic, and array-bounds index checking prevents these bugs from occurring, substantially reducing development time. While a run-time performance penalty must be paid, the only unacceptable performance we encountered was using standard Java serialization to checkpoint and restart the code. This was fixed by a two-day implementation of custom checkpointing. JavaGenes is minimally integrated with Condor; in other words, JavaGenes must do its own checkpointing and I/O redirection. A prototype Java-aware version of Condor was developed using standard Java serialization for checkpointing. For the prototype to be useful, standard Java serialization must be significantly optimized. JavaGenes is approximately 8700 lines of code and a few thousand JavaGenes jobs have been run. Most jobs ran for a few days. Results include proof that genetic algorithms can evolve directed and undirected graphs, development of a novel crossover operator for graphs, a paper in the journal Nanotechnology, and another paper in preparation.

Fiber optic oxygen sensor leak detection system for space applications

NASA Astrophysics Data System (ADS)

Kazemi, Alex A.; Goswami, Kish; Mendoza, Edgar A.; Kempen, Lothar U.

2007-09-01

This paper describes the successful test of a multi-point fiber optic oxygen sensor system during the static firing of an Evolved Expandable Launch Vehicle (EELV)/Delta IV common booster core (CBC) rocket engine at NASA's Stennis Flight Center. The system consisted of microsensors (optrodes) using an oxygen gas sensitive indicator incorporated onto an optically transparent porous substrate. The modular optoelectronics and multiplexing network system was designed and assembled utilizing a multi-channel opto-electronic sensor readout unit that monitored the oxygen and temperature response of the individual optrodes in real-time and communicated this information via a serial communication port to a remote laptop computer. The sensor packaging for oxygen consisted of two optrodes - one doped with an indicator sensitive to oxygen, and the other doped with an indicator sensitive to temperature. The multichannel oxygen sensor system is fully reversible. It has demonstrated a dynamic response to oxygen gas in the range of 0% to 100% with 0.1% resolution and a response time of <=10 seconds. The sensor package was attached to a custom fiber optic ribbon cable, which was then connected to a fiber optic trunk communications cable (standard telecommunications-grade fiber) that connected to the optoelectronics module. Each board in the expandable module included light sources, photo-detectors, and associated electronics required for detecting oxygen and temperature. The paper illustrates the sensor design and performance data under field deployment conditions.

Low Oxygen and Ocean Acidification on the Vancouver Island Shelf

NASA Astrophysics Data System (ADS)

Bianucci, L.; Denman, K.

2008-12-01

In the recent years hypoxic events have been observed along the west coast of North America (off Oregon and California). Although a common cause of coastal hypoxia is usually anthropogenic eutrophication, in these upwelling regions the advection of oxygen-depleted waters from offshore is a key mechanism. Moreover, the high productivity typical of these margins generates a large flux of sinking particular organic matter. The remineralization of this matter below the euphotic zone produces an elevated consumption of oxygen. When concentrations become lower than certain threshold, hypoxia leads to a major change in the ecosystem and the affected areas are called 'dead zones'. Furthermore, the two processes that drive oxygen levels down (physical upwelling and biological demand) also increase dissolved inorganic carbon in the shelf, which leads to a pH reduction. Ocean acidification and hypoxia can severely affect ecosystems, and the links between these phenomena have not been explored. This presentation will discuss a model study of the carbon and oxygen coupling on the Vancouver Island shelf, with focus on the connection between acidification and hypoxia. Moreover, the role of biology versus physics will be investigated. This region comprises the northern end of the wind-driven upwelling margin off western North America, where low oxygen events have not been extensively studied. However, the proximity to an Oxygen Minimum Zone offshore and the observed decline of oxygen in the Northeast Pacific turns this shelf into a potential candidate to suffer from low-oxygen events. The model used is the Regional Ocean Modeling System (ROMS) in a quasi-2D configuration of the shelf (across-shore section with uniform properties alongshore). The biogeochemical model has carbon, oxygen, and nitrogen as state variables, and includes cycling of dissolved organic matter. Carbon and oxygen cycles are coupled through ecosystem processes such as photosynthesis and remineralization, while they are decoupled by other processes (e.g., nitrification and denitrification).

Oxygen cycling in the northern Benguela Upwelling System: Modelling oxygen sources and sinks

NASA Astrophysics Data System (ADS)

Schmidt, Martin; Eggert, Anja

2016-12-01

This paper elucidates the oxygen dynamics in the northern Benguela Upwelling System by means of process oriented, numerical modelling. Owing to the complex physical-biological interaction in this system, a coupled hydrodynamic-biogeochemical model is required to grasp the various aspects of the oxygen dynamics. We used high-resolution atmospheric fields derived from observations to force our model, available since 1999. The model results represent a 15 years, consistent data set of realistic hydrographic and ecosystem variables, including oxygen distribution patterns. After a concise description of the main aspects of the model, we use the model data to analyse the components contributing to the oxygen dynamics, namely, the ocean circulation, the exchange between ocean and atmosphere as well as the local biogeochemical oxygen cycling in the system. We thoroughly validate the model with available field observations and remote sensing data. The strengths of coastal upwelling, which controls the nutrient supply to the euphotic zone, as well as the poleward undercurrent that carries oxygen and nutrients to the shelf in the northern Benguela Upwelling System are well reproduced in the model. Among the biological oxygen sinks, mineralisation in the sediment, respiration of zooplankton and nitrification in the water column are important. We also found that vertical migration of zooplankton in response to the oxygen conditions provides a regulating feedback, which may prevent a complete deoxygenation of suboxic waters. As long as oxygen or nitrate are available in the bottom waters, the activities of chemolithoautotrophic sulphur bacteria on the sediment surface keep the redoxcline within the sediment and prevent the release of hydrogen sulphide into the water column. By horizontal integration of the simulated ocean-atmosphere oxygen flux, it can be shown that the Kunene upwelling cell between 16 ° S and 18 ° S is a boundary between the equatorial ocean, characterise by weak oxygen release to the atmosphere, and the subtropical Benguela Upwelling System governed by an enhanced and seasonal varying flux. Furthermore, a comparison of oxygen fluxes controlled by physical transport versus biogeochemical processes shows that the physical processes dominate in the northern Benguela Upwelling System.

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

DOE PAGES

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; ...

2016-02-03

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

Ultrafast Primary Reactions in the Photosystems of Oxygen-Evolving Organisms

NASA Astrophysics Data System (ADS)

Holzwarth, A. R.

In oxygen-evolving photosynthetic organisms (plants, green algae, cyanobacteria), the primary steps of photosynthesis occur in two membrane-bound protein supercomplexes, Photosystem I (PS I) and Photosystem II (PS II), located in the thylakoid membrane (c.f. Fig. 7.1) along with two other important protein complexes, the cytochrome b6/f complex and the ATP-synthase [1]. Each of the photosystems consists of a reaction center (RC) where the photoinduced early electron transfer processes occur, of a so-called core antenna consisting of chlorophyll (Chl) protein complexes responsible for light absorption and ultrafast energy transfer to the RC pigments, and additional peripheral antenna complexes of various kinds that increase the absorption cross-section. The peripheral complexes are Chl a/b-protein complexes in higher plants and green algae (LHC I or LHC II for PS I or PS II, respectively) and so-called phycobilisomes in cyanobacteria and red algae [2-4]. The structures and light-harvesting functions of these antenna systems have been extensively reviewed [2, 5-9]. Recently, X-ray structures of both PS I and PS II antenna/RC complexes have been determined, some to atomic resolution. Although many details of the pigment content and organization of the RCs and antenna systems of PS I and PS II have been known before, the high resolution structures of the integral complexes allow us for the first time to try to understand structure/function relationships in detail. This article covers our present understanding of the ultrafast energy transfer and early electron transfer processes occurring in the photosystems of oxygen-evolving organisms. The main emphasis will be on the electron transfer processes. However, in both photosystems the kinetics of the energy transfer processes in the core antennae is intimately interwoven with the kinetics of the electron transfer steps. Since both types of processes occur on a similar time scale, their kinetics cannot be considered separately in any experiment and consequently they have to be discussed together.

3D Nitrogen, Sulfur-Codoped Carbon Nanomaterial-Supported Cobalt Oxides with Polyhedron-Like Particles Grafted onto Graphene Layers as Highly Active Bicatalysts for Oxygen-Evolving Reactions.

PubMed

Huang, Xiaobo; Wang, Jianqiang; Bao, Hongliang; Zhang, Xiangkun; Huang, Yongmin

2018-02-28

The extensive research and developments of highly efficient oxygen electrode electrocatalysts to get rid of the kinetic barriers for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are very important in energy conversion and storage devices. Especially, exploring nonprecious metal alternatives to replace traditional noble metal catalysts with high cost and poor durability is the paramount mission. In this paper, we utilize property-flexible ZIF-67 and sulfur-functionalized graphene oxide to obtain a cobalt, nitrogen, and sulfur codoped nanomaterial with 3D hierarchical porous structures, owing to their rich dopant species and good conductivity. The crosslinked structures of polyhedron particles throughout the whole carbon framework speeds up the mass transportation and charge-delivery processes during oxygen-evolving reactions. Also, by exploring the location and coordination type of sulfur dopants, we emphasize the effects of sulfone and sulfide functional groups anchored into the graphitic structure on enhancing the catalytic abilities for ORR and OER. To note, compared to the noble metal electrocatalysts, the best-performing CoO@Co 3 O 4 /NSG-650 (0.79 V) is 40 mV less active than the commercial Pt/C catalyst (0.83 V) for ORR and merely 10 mV behind IrO 2 (1.68 V) for OER. Besides, the metric between ORR and OER difference for CoO@Co 3 O 4 /NSG-650 to evaluate its overall electrocatalytic activity is 0.90 V, surpassing 290 and 430 mV over Pt/C (1.19 V) and IrO 2 (1.33 V). Comprehensively, the as-prepared CoO@Co 3 O 4 /NSG-650 indicates excellent bifunctional catalytic activities for ORR and OER, which shows great potential for replacing noble metal catalysts in the application of fuel cells and metal-air batteries.

How Things Work. Teacher's Guide.

ERIC Educational Resources Information Center

Brown, Mark; And Others

This unit examines the earth's processes and systems from an energy perspective. A technical language for discussion of energy systems is developed. Objectives include the ability of students to discuss earth's carbon/oxygen cycle, hydrological cycle, and heat patterns and the functioning of producers, consumers and decomposers in the environment.…

GEDAE-LaB: A Free Software to Calculate the Energy System Contributions during Exercise

PubMed Central

Bertuzzi, Rômulo; Melegati, Jorge; Bueno, Salomão; Ghiarone, Thaysa; Pasqua, Leonardo A.; Gáspari, Arthur Fernandes; Lima-Silva, Adriano E.; Goldman, Alfredo

2016-01-01

Purpose The aim of the current study is to describe the functionality of free software developed for energy system contributions and energy expenditure calculation during exercise, namely GEDAE-LaB. Methods Eleven participants performed the following tests: 1) a maximal cycling incremental test to measure the ventilatory threshold and maximal oxygen uptake (V˙O2max); 2) a cycling workload constant test at moderate domain (90% ventilatory threshold); 3) a cycling workload constant test at severe domain (110% V˙O2max). Oxygen uptake and plasma lactate were measured during the tests. The contributions of the aerobic (AMET), anaerobic lactic (LAMET), and anaerobic alactic (ALMET) systems were calculated based on the oxygen uptake during exercise, the oxygen energy equivalents provided by lactate accumulation, and the fast component of excess post-exercise oxygen consumption, respectively. In order to assess the intra-investigator variation, four different investigators performed the analyses independently using GEDAE-LaB. A direct comparison with commercial software was also provided. Results All subjects completed 10 min of exercise at moderate domain, while the time to exhaustion at severe domain was 144 ± 65 s. The AMET, LAMET, and ALMET contributions during moderate domain were about 93, 2, and 5%, respectively. The AMET, LAMET, and ALMET contributions during severe domain were about 66, 21, and 13%, respectively. No statistical differences were found between the energy system contributions and energy expenditure obtained by GEDAE-LaB and commercial software for both moderate and severe domains (P > 0.05). The ICC revealed that these estimates were highly reliable among the four investigators for both moderate and severe domains (all ICC ≥ 0.94). Conclusion These findings suggest that GEDAE-LaB is a free software easily comprehended by users minimally familiarized with adopted procedures for calculations of energetic profile using oxygen uptake and lactate accumulation during exercise. By providing availability of the software and its source code we hope to facilitate future related research. PMID:26727499

GEDAE-LaB: A Free Software to Calculate the Energy System Contributions during Exercise.

PubMed

Bertuzzi, Rômulo; Melegati, Jorge; Bueno, Salomão; Ghiarone, Thaysa; Pasqua, Leonardo A; Gáspari, Arthur Fernandes; Lima-Silva, Adriano E; Goldman, Alfredo

2016-01-01

The aim of the current study is to describe the functionality of free software developed for energy system contributions and energy expenditure calculation during exercise, namely GEDAE-LaB. Eleven participants performed the following tests: 1) a maximal cycling incremental test to measure the ventilatory threshold and maximal oxygen uptake (V̇O2max); 2) a cycling workload constant test at moderate domain (90% ventilatory threshold); 3) a cycling workload constant test at severe domain (110% V̇O2max). Oxygen uptake and plasma lactate were measured during the tests. The contributions of the aerobic (AMET), anaerobic lactic (LAMET), and anaerobic alactic (ALMET) systems were calculated based on the oxygen uptake during exercise, the oxygen energy equivalents provided by lactate accumulation, and the fast component of excess post-exercise oxygen consumption, respectively. In order to assess the intra-investigator variation, four different investigators performed the analyses independently using GEDAE-LaB. A direct comparison with commercial software was also provided. All subjects completed 10 min of exercise at moderate domain, while the time to exhaustion at severe domain was 144 ± 65 s. The AMET, LAMET, and ALMET contributions during moderate domain were about 93, 2, and 5%, respectively. The AMET, LAMET, and ALMET contributions during severe domain were about 66, 21, and 13%, respectively. No statistical differences were found between the energy system contributions and energy expenditure obtained by GEDAE-LaB and commercial software for both moderate and severe domains (P > 0.05). The ICC revealed that these estimates were highly reliable among the four investigators for both moderate and severe domains (all ICC ≥ 0.94). These findings suggest that GEDAE-LaB is a free software easily comprehended by users minimally familiarized with adopted procedures for calculations of energetic profile using oxygen uptake and lactate accumulation during exercise. By providing availability of the software and its source code we hope to facilitate future related research.

Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

NASA Astrophysics Data System (ADS)

Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

2016-03-01

Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

PubMed

Leshin, L A; Mahaffy, P R; Webster, C R; Cabane, M; Coll, P; Conrad, P G; Archer, P D; Atreya, S K; Brunner, A E; Buch, A; Eigenbrode, J L; Flesch, G J; Franz, H B; Freissinet, C; Glavin, D P; McAdam, A C; Miller, K E; Ming, D W; Morris, R V; Navarro-González, R; Niles, P B; Owen, T; Pepin, R O; Squyres, S; Steele, A; Stern, J C; Summons, R E; Sumner, D Y; Sutter, B; Szopa, C; Teinturier, S; Trainer, M G; Wray, J J; Grotzinger, J P

2013-09-27

Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.