Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

Science.gov (United States)

Shevela, Dmitriy; Koroidov, Sergey; Najafpour, M Mahdi; Messinger, Johannes; Kurz, Philipp

2011-05-02

Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanisms controlling the oxygen consumption in experimentally induced hypochloremic alkalosis in calves.

Science.gov (United States)

Cambier, Carole; Clerbaux, Thierry; Amory, Hélène; Detry, Bruno; Florquin, Sandra; Marville, Vincent; Frans, Albert; Gustin, Pascal

2002-01-01

The study was carried out on healthy Friesian calves (n = 10) aged between 10 and 30 days. Hypochloremia and alkalosis were induced by intravenous administration of furosemide and isotonic sodium bicarbonate. The venous and arterial blood samples were collected repeatedly. 2,3-diphosphoglycerate (2,3-DPG), hemoglobin and plasmatic chloride concentrations were determined. The red blood cell chloride concentration was also calculated. pH, PCO2 and PO2 were measured in arterial and mixed venous blood. The oxygen equilibrium curve (OEC) was measured in standard conditions. The correspondence of the OEC to the arterial and mixed venous compartments was calculated, taking blood temperature, pH and PCO2 values into account. The oxygen exchange fraction (OEF%), corresponding to the degree of blood desaturation between the arterial and mixed venous compartments and the amount of oxygen released at the tissue level by 100 mL of blood (OEF Vol%) were calculated from the arterial and mixed venous OEC, combined with PO2 and hemoglobin concentration. Oxygen delivery (DO2) was calculated using the arterial oxygen content, the cardiac output measured by thermodilution, and the body weight of the animal. The oxygen consumption (VO2) was derived from the cardiac output, OEF Vol% and body weight values. Despite the plasma hypochloremia, the erythrocyte chloride concentration was not influenced by furosemide and sodium bicarbonate infusion. Due to the alkalosis-induced increase in the 2,3-DPG, the standard OEC was shifted to the right, allowing oxygen to dissociate from hemoglobin more rapidly. These changes opposed the increased affinity of hemoglobin for oxygen induced by alkalosis. Moreover, respiratory acidosis, hemoconcentration, and the slight decrease in the partial oxygen pressure in mixed venous blood (Pvo2) tended to improve the OEF Vol% and maintain the oxygen consumption in a physiological range while the cardiac output, and the oxygen delivery were significantly decreased

Photosynthetic water oxidation: binding and activation of substrate waters for O-O bond formation.

Science.gov (United States)

Vinyard, David J; Khan, Sahr; Brudvig, Gary W

2015-01-01

Photosynthetic water oxidation occurs at the oxygen-evolving complex (OEC) of Photosystem II (PSII). The OEC, which contains a Mn4CaO5 inorganic cluster ligated by oxides, waters and amino-acid residues, cycles through five redox intermediates known as S(i) states (i = 0-4). The electronic and structural properties of the transient S4 intermediate that forms the O-O bond are not well understood. In order to gain insight into how water is activated for O-O bond formation in the S4 intermediate, we have performed a detailed analysis of S-state dependent substrate water binding kinetics taking into consideration data from Mn coordination complexes. This analysis supports a model in which the substrate waters are both bound as terminal ligands and react via a water-nucleophile attack mechanism.

Characterization of the Sr(2+)- and Cd(2+)-Substituted Oxygen-Evolving Complex of Photosystem II by Quantum Mechanics/Molecular Mechanics Calculations.

Science.gov (United States)

Pitari, Fabio; Bovi, Daniele; Narzi, Daniele; Guidoni, Leonardo

2015-09-29

The Mn4CaO5 cluster in the oxygen-evolving complex is the catalytic core of the Photosystem II (PSII) enzyme, responsible for the water splitting reaction in oxygenic photosynthesis. The role of the redox-inactive ion in the cluster has not yet been fully clarified, although several experimental data are available on Ca2+-depleted and Ca2+-substituted PSII complexes, indicating Sr2+-substituted PSII as the only modification that preserves oxygen evolution. In this work, we investigated the structural and electronic properties of the PSII catalytic core with Ca2+ replaced with Sr2+ and Cd2+ in the S2 state of the Kok−Joliot cycle by means of density functional theory and ab initio molecular dynamics based on a quantum mechanics/ molecular mechanics approach. Our calculations do not reveal significant differences between the substituted and wild-type systems in terms of geometries, thermodynamics, and kinetics of two previously identified intermediate states along the S2 to S3 transition, namely, the open cubane S2 A and closed cubane S2 B conformers. Conversely, our calculations show different pKa values for the water molecule bound to the three investigated heterocations. Specifically, for Cd-substituted PSII, the pKa value is 5.3 units smaller than the respective value in wild type Ca-PSII. On the basis of our results, we conclude that, assuming all the cations sharing the same binding site, the induced difference in the acidity of the binding pocket might influence the hydrogen bonding network and the redox levels to prevent the further evolution of the cycle toward the S3 state.

Ranking in evolving complex networks

Science.gov (United States)

Liao, Hao; Mariani, Manuel Sebastian; Medo, Matúš; Zhang, Yi-Cheng; Zhou, Ming-Yang

2017-05-01

Complex networks have emerged as a simple yet powerful framework to represent and analyze a wide range of complex systems. The problem of ranking the nodes and the edges in complex networks is critical for a broad range of real-world problems because it affects how we access online information and products, how success and talent are evaluated in human activities, and how scarce resources are allocated by companies and policymakers, among others. This calls for a deep understanding of how existing ranking algorithms perform, and which are their possible biases that may impair their effectiveness. Many popular ranking algorithms (such as Google's PageRank) are static in nature and, as a consequence, they exhibit important shortcomings when applied to real networks that rapidly evolve in time. At the same time, recent advances in the understanding and modeling of evolving networks have enabled the development of a wide and diverse range of ranking algorithms that take the temporal dimension into account. The aim of this review is to survey the existing ranking algorithms, both static and time-aware, and their applications to evolving networks. We emphasize both the impact of network evolution on well-established static algorithms and the benefits from including the temporal dimension for tasks such as prediction of network traffic, prediction of future links, and identification of significant nodes.

Experimental study on the influence of oxygen content in the combustion air on the combustion characteristics

International Nuclear Information System (INIS)

Bělohradský, Petr; Skryja, Pavel; Hudák, Igor

2014-01-01

This study was focused on the experimental investigation of the very promising combustion technology called as the oxygen-enhanced combustion (OEC), which uses the oxidant containing higher proportion of oxygen than in the atmospheric air, i.e. more than 21%. The work investigated and compared the characteristics of two OEC methods, namely the premix enrichment and air-oxy/fuel combustion, when the overall oxygen concentration was varied from 21% to 46%. The combustion tests were performed with the experimental two-gas-staged burner of low-NO x type at the burner thermal input of 750 kW for two combustion regimes – one-staged and two-staged combustion. The oxygen concentration in the flue gas was maintained in the neighborhood of 3% vol. (on dry basis). The aim of tests was to assess the impact of the oxidant composition, type of OEC method and fuel-staging on the characteristic combustion parameters in detail. The investigated parameters included the concentration of nitrogen oxides (NO x ) in the flue gas, flue gas temperature, heat flux to the combustion chamber wall, and lastly the stability, shape and dimensions of flame. It was observed that NO x emission is significantly lower when the air-oxy/fuel method is used compared to the premix enrichment method. Moreover, when the fuel was staged, NO x emission was below 120 mg/Nm 3 at all investigated oxygen flow rates. Increasing oxygen concentration resulted in higher heating intensity due to higher concentrations of CO 2 and H 2 O. The available heat at 46% O 2 was higher by 20% compared with that at 21% O 2 . - Highlights: • Premix-enrichment and air-oxy/fuel combustion methods were experimentally studied. • NO x increased sharply as oxygen concentration increased during PE tests. • NO x was below 120 mg/Nm 3 for all investigated oxygen flow rates in AO tests. • Radiative heat transfer was enhanced ca. 20% as O 2 concentration was increased. • OEC flames were observed stable, more luminous and

Light Driven Energy Research at LCLS: Planned Pump-Probe X-ray Spectroscopy Studies on Photosynthetic Water Splitting

Science.gov (United States)

Bergmann, Uwe

2010-02-01

Arguably the most important chemical reaction on earth is the photosynthetic splitting of water to molecular oxygen by the Mn-containing oxygen-evolving complex (Mn-OEC) in the protein known as photosystem II (PSII). It is this reaction which has, over the course of some 3.8 billion years, gradually filled our atmosphere with O2 and consequently enabled and sustained the evolution of complex aerobic life. Coupled to the reduction of carbon dioxide, biological photosynthesis contributes foodstuffs for nutrition while recycling CO2 from the atmosphere and replacing it with O2. By utilizing sunlight to power these energy-requiring reactions, photosynthesis also serves as a model for addressing societal energy needs as we enter an era of diminishing fossil hydrocarbon resources. Understanding, at the molecular level, the dynamics and mechanism of how nature has solved this problem is of fundamental importance and could be critical to aid in the design of manufactured devices to accomplish the conversion of sunlight into useful electrochemical energy and transportable fuel in the foreseeable future. In order to understand the photosynthetic splitting of water by the Mn-OEC we need to be able to follow the reaction in real time at an atomic level. A powerful probe to study the electronic and molecular structure of the Mn-OEC is x-ray spectroscopy. Here, in particular x-ray emission spectroscopy (XES) has two crucial qualities for LCLS based time-dependent pump-probe studies of the Mn-OEC: a) it directly probes the Mn oxidation state and ligation, b) it can be performed with wavelength dispersive optics to avoid the necessity of scanning in pump probe experiments. Recent results and the planned time dependent experiments at LCLS will be discussed. )

Response of Lemna minor L. to short-term cobalt exposure: The effect on photosynthetic electron transport chain and induction of oxidative damage.

Science.gov (United States)

Begović, Lidija; Mlinarić, Selma; Antunović Dunić, Jasenka; Katanić, Zorana; Lončarić, Zdenko; Lepeduš, Hrvoje; Cesar, Vera

2016-06-01

The effect of two concentrations of cobalt (Co(2+)) on photosynthetic activity and antioxidative response in Lemna minor L. were assessed 24, 48 and 72h after the start of the exposure. Higher concentration of cobalt (1mM) induced growth inhibition while lower concentration (0.01mM) increased photosynthetic pigments content. Analysis of chlorophyll a fluorescence transients revealed high sensitivity of photosystem II primary photochemistry to excess of Co(2+) especially at the higher concentration where decreased electron transport beyond primary quinone acceptor QA(-) and impaired function of oxygen evolving complex (OEC) was observed. Due to impairment of OEC, oxygen production was decreased at higher Co(2+) concentration. Activity of superoxide dismutase was mainly inhibited while lipid peroxidation increased, at both concentrations, indicating that cobalt-induced oxidative damage after short exposure and moreover, susceptibility of the membranes in the cell to cobalt toxicity. Results obtained in this study suggest possible application of used parameters as tools in assessment of early damage caused by metals. Copyright © 2016 Elsevier B.V. All rights reserved.

Functional and structural analysis of photosystem II core complexes from spinach with high oxygen evolution capacity

NARCIS (Netherlands)

Haag, Elisabeth; Irrgang, Klaus-D.; Boekema, Egbert J.; Renger, Gernot

1990-01-01

Oxygen-evolving photo system II core complexes were prepared from spinach by solubilizing photosystem II membrane fragments with dodecyl-β-D-maltoside. The core complexes consist of the intrinsic 47-kDa, 43-kDa, D1 and D2 polypeptides, the two subunits of cytochrome b559 and the extrinsic 33-kDa

X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

Energy Technology Data Exchange (ETDEWEB)

Andrews, J.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Structural Biology Div.

1995-08-01

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 II 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.

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

Science.gov (United States)

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.

Improvements in serial femtosecond crystallography of photosystem II by optimizing crystal uniformity using microseeding procedures

International Nuclear Information System (INIS)

Ibrahim, Mohamed; Yachandra, Vittal K.; Yano, Junko; Kern, Jan; Zouni, Athina; Technische Univ. Berlin

2015-01-01

In photosynthesis, photosystem II (PSII) is the multi-subunit membrane protein complex that catalyzes photo-oxidation of water into dioxygen through the oxygen evolving complex (OEC). To understand the water oxidation reaction, it is important to get structural information about the transient and intermediate states of the OEC in the dimeric PSII core complex (dPSIIcc). In recent times, femtosecond X-ray pulses from the free electron laser (XFEL) are being used to obtain X-ray diffraction (XRD) data of dPSIIcc microcrystals at room temperature that are free of radiation damage. In our experiments at the XFEL, we used an electrospun liquid microjet setup that requires microcrystals less than 40 μm in size. In this study, we explored various microseeding techniques to get a high yield of monodisperse uniform-sized microcrystals. Monodisperse microcrystals of dPSIIcc of uniform size were a key to improve the stability of the jet and the quality of XRD data obtained at the XFEL. This was evident by an improvement of the quality of the datasets obtained, from 6.5 Å, using crystals grown without the micro seeding approach, to 4.5 Å using crystals generated with the new method

Improvements in serial femtosecond crystallography of photosystem II by optimizing crystal uniformity using microseeding procedures.

Science.gov (United States)

Ibrahim, Mohamed; Chatterjee, Ruchira; Hellmich, Julia; Tran, Rosalie; Bommer, Martin; Yachandra, Vittal K; Yano, Junko; Kern, Jan; Zouni, Athina

In photosynthesis, photosystem II (PSII) is the multi-subunit membrane protein complex that catalyzes photo-oxidation of water into dioxygen through the oxygen evolving complex (OEC). To understand the water oxidation reaction, it is important to get structural information about the transient and intermediate states of the OEC in the dimeric PSII core complex (dPSIIcc). In recent times, femtosecond X-ray pulses from the free electron laser (XFEL) are being used to obtain X-ray diffraction (XRD) data of dPSIIcc microcrystals at room temperature that are free of radiation damage. In our experiments at the XFEL, we used an electrospun liquid microjet setup that requires microcrystals less than 40 μ m in size. In this study, we explored various microseeding techniques to get a high yield of monodisperse uniform-sized microcrystals. Monodisperse microcrystals of dPSIIcc of uniform size were a key to improve the stability of the jet and the quality of XRD data obtained at the XFEL. This was evident by an improvement of the quality of the datasets obtained, from 6.5Å, using crystals grown without the micro seeding approach, to 4.5Å using crystals generated with the new method.

Influence of Plio-Pleistocene basin hydrology on the Turkana hominin enamel carbonate δ(18)O values.

Science.gov (United States)

Quinn, Rhonda L

2015-09-01

Stable oxygen isotopes of hominin enamel carbonate (δ(18)OEC) provide a window into aspects of past drinking behavior and diet, body size, breastfeeding and weaning, mobility, and paleoclimate. It is tempting to compare all hominins across time and space in order to gauge species-level adaptations to changing environments and niche separation between those living sympatrically. Basinal, sub-basinal, and micro-environmental differences, however, may exert an influence on variation in enamel carbonate isotopic values that must be reconciled before hominin species across Africa can be meaningfully compared. Plio-Pleistocene Turkana hominin δ(18)OEC values show a considerable spread, potentially revealing many intrinsic and extrinsic contributing factors operating on different scales. In this study, I examine Turkana hominin δ(18)OEC values relative to identity (taxon, tooth type and number, body size of taxon), dietary (δ(13)C value, Turkana coeval and modern mammalian δ(18)OEC values), and contextual (time, depositional environment) information of each specimen and collection locality and discuss various potential influences. Turkana hominin δ(18)OEC values may primarily reflect differences in imbibed water sources (lake vs. river) as a function of evolving basin hydrology. Copyright © 2015 Elsevier Ltd. All rights reserved.

Open-Ended Behavioral Complexity for Evolved Virtual Creatures

DEFF Research Database (Denmark)

Lessin, Dan; Fussell, Don; Miikkulainen, Risto

2013-01-01

notable exception to this progress. Despite the potential benefits, there has been no clear increase in the behavioral complexity of evolved virtual creatures (EVCs) beyond the light following demonstrated in Sims' original work. This paper presents an open-ended method to move beyond this limit, making...... creature with behavioral complexity that clearly exceeds previously achieved levels. ESP thus demonstrates that EVCs may indeed have the potential to one day rival the behavioral complexity--and therefore the entertainment value--of their non-virtual counterparts....

X-ray spectroscopy of the photosynthetic oxygen-evolving complex

Energy Technology Data Exchange (ETDEWEB)

Sauer, Ken; Yano, Junko; Yachandra, Vittal K

2007-04-05

Water oxidation to dioxygen in photosynthesis is catalyzed by a Mn4Ca cluster with O bridging in Photosystem II (PS II) of plants, algae and cyanobacteria. A variety of spectroscopic methods have been applied to analyzing the participation of the complex. X-ray spectroscopy is particularly useful because it is element-specific, and because it can reveal important structural features of the complex with high accuracy and identify the participation of Mn in the redox chemistry. Following a brief history of the application of X-ray spectroscopy to PS II, an overview of newer results will be presented and a description of the present state of our knowledge based on this approach.

Degeneracy: a link between evolvability, robustness and complexity in biological systems

Directory of Open Access Journals (Sweden)

Whitacre James M

2010-02-01

Full Text Available Abstract A full accounting of biological robustness remains elusive; both in terms of the mechanisms by which robustness is achieved and the forces that have caused robustness to grow over evolutionary time. Although its importance to topics such as ecosystem services and resilience is well recognized, the broader relationship between robustness and evolution is only starting to be fully appreciated. A renewed interest in this relationship has been prompted by evidence that mutational robustness can play a positive role in the discovery of adaptive innovations (evolvability and evidence of an intimate relationship between robustness and complexity in biology. This paper offers a new perspective on the mechanics of evolution and the origins of complexity, robustness, and evolvability. Here we explore the hypothesis that degeneracy, a partial overlap in the functioning of multi-functional components, plays a central role in the evolution and robustness of complex forms. In support of this hypothesis, we present evidence that degeneracy is a fundamental source of robustness, it is intimately tied to multi-scaled complexity, and it establishes conditions that are necessary for system evolvability.

Polyurethane/Polylactide-Blend Films Doped with Zinc Ions for the Growth and Expansion of Human Olfactory Ensheathing Cells (OECs and Adipose-Derived Mesenchymal Stromal Stem Cells (ASCs for Regenerative Medicine Applications

Directory of Open Access Journals (Sweden)

Krzysztof Marycz

2016-04-01

Full Text Available Polymeric biomaterials based on polyurethane and polylactide blends are promising candidates for regenerative medicine applications as biocompatible, bioresorbable carriers. In current research we showed that 80/20 polyurethane/polylactide blends (PU/PLDL with confirmed biological properties in vitro may be further improved by the addition of ZnO nanoparticles for the delivery of bioactive zinc oxide for cells. The PU/PLDL blends were doped with different concentrations of ZnO (0.001%, 0.01%, 0.05% and undertaken for in vitro biological evaluation using human adipose stromal stem cells (ASCs and olfactory ensheathing cells (OECs. The addition of 0.001% of ZnO to the biomaterials positively influenced the morphology, proliferation, and phenotype of cells cultured on the scaffolds. Moreover, the analysis of oxidative stress markers revealed that 0.001% of ZnO added to the material decreased the stress level in both cell lines. In addition, the levels of neural-specific genes were upregulated in OECs when cultured on sample 0.001 ZnO, while the apoptosis-related genes were downregulated in OECs and ASCs in the same group. Therefore, we showed that PU/PLDL blends doped with 0.001% of ZnO exert beneficial influence on ASCs and OECs in vitro and they may be considered for future applications in the field of regenerative medicine.

Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

Energy Technology Data Exchange (ETDEWEB)

Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

2002-08-02

The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

Manganese Loading and Photosystem II Stability are Key Components of Manganese Efficiency in Plants

DEFF Research Database (Denmark)

Schmidt, Sidsel Birkelund

Manganese (Mn) deficiency constitutes a major plant nutritional problem in commercial crop production of winter cereals. In plants, Mn has an indispensable role in the oxygen evolving complex (OEC) of photosystem II (PSII). Hence, the consequences of Mn deficiency are reduced plant growth......, and eventually substantial yield losses. It is well known, that genotypes within plant species differ considerably in tolerance to growth under Mn limiting conditions, a phenomenon designated as Mn efficiency. However, the physiological responses reflecting the underlying mechanisms of Mn efficiency are still...... not fully understood. In this PhD study, a new method for determination and characterization of metal binding in size-fractionated photosynthetic protein complexes from barley thylakoids was established. The applicability of the method was shown by quantification of Mn binding in PSII from thylakoids of two...

Chemical complexity in the winds of the oxygen-rich supergiant star VY Canis Majoris

Science.gov (United States)

Ziurys, L. M.; Milam, S. N.; Apponi, A. J.; Woolf, N. J.

2007-06-01

The interstellar medium is enriched primarily by matter ejected from old, evolved stars. The outflows from these stars create spherical envelopes, which foster gas-phase chemistry. The chemical complexity in circumstellar shells was originally thought to be dominated by the elemental carbon to oxygen ratio. Observations have suggested that envelopes with more carbon than oxygen have a significantly greater abundance of molecules than their oxygen-rich analogues. Here we report observations of molecules in the oxygen-rich shell of the red supergiant star VY Canis Majoris (VY CMa). A variety of unexpected chemical compounds have been identified, including NaCl, PN, HNC and HCO+. From the spectral line profiles, the molecules can be distinguished as arising from three distinct kinematic regions: a spherical outflow, a tightly collimated, blue-shifted expansion, and a directed, red-shifted flow. Certain species (SiO, PN and NaCl) exclusively trace the spherical flow, whereas HNC and sulphur-bearing molecules (amongst others) are selectively created in the two expansions, perhaps arising from shock waves. CO, HCN, CS and HCO+ exist in all three components. Despite the oxygen-rich environment, HCN seems to be as abundant as CO. These results suggest that oxygen-rich shells may be as chemically diverse as their carbon counterparts.

Circumstellar ammonia in oxygen-rich evolved stars

Science.gov (United States)

Wong, K. T.; Menten, K. M.; Kamiński, T.; Wyrowski, F.; Lacy, J. H.; Greathouse, T. K.

2018-04-01

Context. The circumstellar ammonia (NH3) chemistry in evolved stars is poorly understood. Previous observations and modelling showed that NH3 abundance in oxygen-rich stars is several orders of magnitude above that predicted by equilibrium chemistry. Aims: We would like to characterise the spatial distribution and excitation of NH3 in the oxygen-rich circumstellar envelopes (CSEs) of four diverse targets: IK Tau, VY CMa, OH 231.8+4.2, and IRC +10420. Methods: We observed NH3 emission from the ground state in the inversion transitions near 1.3 cm with the Very Large Array (VLA) and submillimetre rotational transitions with the Heterodyne Instrument for the Far-Infrared (HIFI) aboard Herschel Space Observatory from all four targets. For IK Tau and VY CMa, we observed NH3 rovibrational absorption lines in the ν2 band near 10.5 μm with the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). We also attempted to search for the rotational transition within the excited vibrational state (v2 = 1) near 2 mm with the IRAM 30m Telescope. Non-LTE radiative transfer modelling, including radiative pumping to the vibrational state, was carried out to derive the radial distribution of NH3 in the CSEs of these targets. Results: We detected NH3 inversion and rotational emission in all four targets. IK Tau and VY CMa show blueshifted absorption in the rovibrational spectra. We did not detect vibrationally excited rotational transition from IK Tau. Spatially resolved VLA images of IK Tau and IRC +10420 show clumpy emission structures; unresolved images of VY CMa and OH 231.8+4.2 indicate that the spatial-kinematic distribution of NH3 is similar to that of assorted molecules, such as SO and SO2, that exhibit localised and clumpy emission. Our modelling shows that the NH3 abundance relative to molecular hydrogen is generally of the order of 10-7, which is a few times lower than previous estimates that were made without considering radiative

Evolving Oxygen Landscape of the Early Atmosphere and Oceans

Science.gov (United States)

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

2013-12-01

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.

Structure of photosystem II and substrate binding at room temperature.

Science.gov (United States)

Young, Iris D; Ibrahim, Mohamed; Chatterjee, Ruchira; Gul, Sheraz; Fuller, Franklin; Koroidov, Sergey; Brewster, Aaron S; Tran, Rosalie; Alonso-Mori, Roberto; Kroll, Thomas; Michels-Clark, Tara; Laksmono, Hartawan; Sierra, Raymond G; Stan, Claudiu A; Hussein, Rana; Zhang, Miao; Douthit, Lacey; Kubin, Markus; de Lichtenberg, Casper; Long Vo, Pham; Nilsson, Håkan; Cheah, Mun Hon; Shevela, Dmitriy; Saracini, Claudio; Bean, Mackenzie A; Seuffert, Ina; Sokaras, Dimosthenis; Weng, Tsu-Chien; Pastor, Ernest; Weninger, Clemens; Fransson, Thomas; Lassalle, Louise; Bräuer, Philipp; Aller, Pierre; Docker, Peter T; Andi, Babak; Orville, Allen M; Glownia, James M; Nelson, Silke; Sikorski, Marcin; Zhu, Diling; Hunter, Mark S; Lane, Thomas J; Aquila, Andy; Koglin, Jason E; Robinson, Joseph; Liang, Mengning; Boutet, Sébastien; Lyubimov, Artem Y; Uervirojnangkoorn, Monarin; Moriarty, Nigel W; Liebschner, Dorothee; Afonine, Pavel V; Waterman, David G; Evans, Gwyndaf; Wernet, Philippe; Dobbek, Holger; Weis, William I; Brunger, Axel T; Zwart, Petrus H; Adams, Paul D; Zouni, Athina; Messinger, Johannes; Bergmann, Uwe; Sauter, Nicholas K; Kern, Jan; Yachandra, Vittal K; Yano, Junko

2016-12-15

Light-induced oxidation of water by photosystem II (PS II) in plants, algae and cyanobacteria has generated most of the dioxygen in the atmosphere. PS II, a membrane-bound multi-subunit pigment protein complex, couples the one-electron photochemistry at the reaction centre with the four-electron redox chemistry of water oxidation at the Mn 4 CaO 5 cluster in the oxygen-evolving complex (OEC). Under illumination, the OEC cycles through five intermediate S-states (S 0 to S 4 ), in which S 1 is the dark-stable state and S 3 is the last semi-stable state before O-O bond formation and O 2 evolution. A detailed understanding of the O-O bond formation mechanism remains a challenge, and will require elucidation of both the structures of the OEC in the different S-states and the binding of the two substrate waters to the catalytic site. Here we report the use of femtosecond pulses from an X-ray free electron laser (XFEL) to obtain damage-free, room temperature structures of dark-adapted (S 1 ), two-flash illuminated (2F; S 3 -enriched), and ammonia-bound two-flash illuminated (2F-NH 3 ; S 3 -enriched) PS II. Although the recent 1.95 Å resolution structure of PS II at cryogenic temperature using an XFEL provided a damage-free view of the S 1 state, measurements at room temperature are required to study the structural landscape of proteins under functional conditions, and also for in situ advancement of the S-states. To investigate the water-binding site(s), ammonia, a water analogue, has been used as a marker, as it binds to the Mn 4 CaO 5 cluster in the S 2 and S 3 states. Since the ammonia-bound OEC is active, the ammonia-binding Mn site is not a substrate water site. This approach, together with a comparison of the native dark and 2F states, is used to discriminate between proposed O-O bond formation mechanisms.

Manganese deficiency in plants

DEFF Research Database (Denmark)

Schmidt, Sidsel Birkelund; Jensen, Poul Erik; Husted, Søren

2016-01-01

Manganese (Mn) is an essential plant micronutrient with an indispensable function as a catalyst in the oxygen-evolving complex (OEC) of photosystem II (PSII). Even so, Mn deficiency frequently occurs without visual leaf symptoms, thereby masking the distribution and dimension of the problem...... restricting crop productivity in many places of the world. Hence, timely alleviation of latent Mn deficiency is a challenge in promoting plant growth and quality. We describe here the key mechanisms of Mn deficiency in plants by focusing on the impact of Mn on PSII stability and functionality. We also address...... the mechanisms underlying the differential tolerance towards Mn deficiency observed among plant genotypes, which enable Mn-efficient plants to grow on marginal land with poor Mn availability....

Biogeochemical Modeling of the Second Rise of Oxygen

Science.gov (United States)

Smith, M. L.; Catling, D.; Claire, M.; Zahnle, K.

2014-03-01

The rise of atmospheric oxygen set the tempo for the evolution of complex life on Earth. Oxygen levels are thought to have increased in two broad steps: one step occurred in the Archean ~ 2.45 Ga (the Great Oxidation Event or GOE), and another step occured in the Neoproterozoic ~750-580 Ma (the Neoprotoerozoic Oxygenation Event or NOE). During the NOE, oxygen levels increased from ~1-10% of the present atmospheric level (PAL) (Holland, 2006), to ~15% PAL in the late Neoproterozoic, to ~100% PAL later in the Phanerozoic. Complex life requires O2, so this transition allowed complex life to evolve. We seek to understand what caused the NOE. To explore causes for the NOE, we build upon the biogeochemical model of Claire et al. (2006), which calculates the redox evolution of the atmosphere, ocean, biosphere, and crust in the Archean through to the early Proterozoic. In this model, the balance between oxygenconsuming and oyxgen-producing fluxes evolves over time such that at ~2.4 Ga, the rapidly acting sources of oxygen outweigh the rapidly-acting sinks. Or, in other words, at ~2.4 Ga, the flux of oxygen from organic carbon burial exceeds the sinks of oxygen from reaction with reduced volcanic and metamoprphic gases. The model is able to drive oxygen levels to 1-10% PAL in the Proterozoic; however, the evolving redox fluxes in the model cannot explain how oxygen levels pushed above 1-10% in the late Proterozoic. The authors suggest that perhaps another buffer, such as sulfur, is needed to describe Proterozoic and Phanerozoic redox evolution. Geologic proxies show that in the Proterozoic, up to 10% of the deep ocean may have been sulfidic. With this ocean chemistry, the global sulfur cycle would have worked differently than it does today. Because the sulfur and oxygen cycles interact, the oxygen concentration could have permanently changed due to an evolving sulfur cycle (in combination with evolving redox fluxes associated with other parts of the oxygen cycle and carbon

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry

International Nuclear Information System (INIS)

Herlory, Olivier; Bonzom, Jean-Marc; Gilbin, Rodolphe

2013-01-01

Highlights: •Our study addressed the toxicity thresholds of uranium on microalgae using PAM fluorometry. •The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium. •Uranium impaired the electron flux between the photosystems until almost complete inhibition. •Non-photochemical quenching was identified as the most sensitive fluorescence parameter. •PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response. -- Abstract: Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5 h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F 0 /F v . Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency (F ′ q /F ′ m , EC 50 = 303 ± 64 μg U L −1 after 5 h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC 50 = 142 ± 98 μg U L −1 after 5 h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown that parameters which stemmed from

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

OpenAIRE

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-01-01

Spin-dependent relaxation and recombination processes in $\\gamma$-irradiated $n$-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, t...

HIV seroprevalence among male prison inmates in the six countries of the Organization of Eastern Caribbean states in the Caribbean (OECS).

Science.gov (United States)

Boisson, E V; Trotman, C

2009-03-01

To determine HIV prevalence among male prison inmates in the six OECS countries in the Caribbean. Six unlinked, anonymous point prevalence surveys of a total of 1288 male inmates were conducted during a one-year period, August 2004 - August 2005. An oral fluid sample was collected and an interviewer-administered questionnaire and consent form was completed for each survey participant. The overall HIV prevalence was 2.8% (range 2.0-4.1%). Only 39% of all inmates had previously been tested, compared to 67% of the HIV-positive inmates. Of all inmates who previously tested, 61% had their last test less than two years ago, 45% had done so while in prison and 39% had done so in a hospital. Most of those who had not previously been tested had no particular reason for not doing so (57%); 24% of them felt it was not necessary or they were not at risk. HIV prevalence among male prison inmates was three times higher than the estimated OECS population prevalence in 2003, slightly higher than the prevalence among incarcerated males in the United States of America and Canada, and lower than that in other Caribbean countries in earlier years. Health information on prison populations is important as this is a vulnerable group, with frequent movement in and out of the general population. Preventative services, voluntary counselling and testing, and appropriate care and treatment should be available to all inmates as this is an opportunity for many who may not otherwise access these services.

Why O2 is required by complex life on habitable planets and the concept of planetary "oxygenation time".

Science.gov (United States)

Catling, David C; Glein, Christopher R; Zahnle, Kevin J; McKay, Christopher P

2005-06-01

Life is constructed from a limited toolkit: the Periodic Table. The reduction of oxygen provides the largest free energy release per electron transfer, except for the reduction of fluorine and chlorine. However, the bonding of O2 ensures that it is sufficiently stable to accumulate in a planetary atmosphere, whereas the more weakly bonded halogen gases are far too reactive ever to achieve significant abundance. Consequently, an atmosphere rich in O2 provides the largest feasible energy source. This universal uniqueness suggests that abundant O2 is necessary for the high-energy demands of complex life anywhere, i.e., for actively mobile organisms of approximately 10(-1)-10(0) m size scale with specialized, differentiated anatomy comparable to advanced metazoans. On Earth, aerobic metabolism provides about an order of magnitude more energy for a given intake of food than anaerobic metabolism. As a result, anaerobes do not grow beyond the complexity of uniseriate filaments of cells because of prohibitively low growth efficiencies in a food chain. The biomass cumulative number density, n, at a particular mass, m, scales as n (> m) proportional to m(-1) for aquatic aerobes, and we show that for anaerobes the predicted scaling is n proportional to m (-1.5), close to a growth-limited threshold. Even with aerobic metabolism, the partial pressure of atmospheric O2 (P(O2)) must exceed approximately 10(3) Pa to allow organisms that rely on O2 diffusion to evolve to a size approximately 10(3) m x P(O2) in the range approximately 10(3)-10(4) Pa is needed to exceed the threshold of approximately 10(2) m size for complex life with circulatory physiology. In terrestrial life, O(2) also facilitates hundreds of metabolic pathways, including those that make specialized structural molecules found only in animals. The time scale to reach P(O(2)) approximately 10(4) Pa, or "oxygenation time," was long on the Earth (approximately 3.9 billion years), within almost a factor of 2 of the Sun

Photorelease of triplet and singlet oxygen from dioxygen complexes

Czech Academy of Sciences Publication Activity Database

Wagnerová, Dana Marie; Lang, Kamil

2011-01-01

Roč. 255, 23-24 (2011), s. 2904-2911 ISSN 0010-8545 R&D Projects: GA ČR GAP207/10/1447; GA ČR GAP208/10/1678 Institutional research plan: CEZ:AV0Z40320502 Keywords : singlet oxygen * triplet oxygen * photochemical elimination * photorelease * Dioxygen complex Subject RIV: CA - Inorganic Chemistry Impact factor: 12.110, year: 2011

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry

Energy Technology Data Exchange (ETDEWEB)

Herlory, Olivier, E-mail: olivier.herlory@gmail.com [IRSN-Laboratoire d’Ecotoxicologie des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France); Bonzom, Jean-Marc, E-mail: jean-marc.bonzom@irsn.fr [IRSN-Laboratoire d’Ecotoxicologie des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France); Gilbin, Rodolphe, E-mail: rodolphe.gilbin@irsn.fr [IRSN-Laboratoire de Biogéochimie, Biodisponibilité et Transferts des Radionucléides, Centre de Cadarache, BP3, 13115 Saint Paul lez Durance (France)

2013-09-15

Highlights: •Our study addressed the toxicity thresholds of uranium on microalgae using PAM fluorometry. •The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium. •Uranium impaired the electron flux between the photosystems until almost complete inhibition. •Non-photochemical quenching was identified as the most sensitive fluorescence parameter. •PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response. -- Abstract: Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5 h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F{sub 0}/F{sub v}. Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency (F{sup ′}{sub q}/F{sup ′}{sub m}, EC{sub 50} = 303 ± 64 μg U L{sup −1} after 5 h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC{sub 50} = 142 ± 98 μg U L{sup −1} after 5 h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown

Molecular Evolution of the Oxygen-Binding Hemerythrin Domain.

Directory of Open Access Journals (Sweden)

Claudia Alvarez-Carreño

Full Text Available 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.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.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

Photosystem II functionality in barley responds dynamically to changes in leaf manganese status

Directory of Open Access Journals (Sweden)

Sidsel Birkelund Schmidt

2016-11-01

Full Text Available A catalytic manganese (Mn cluster is required for the oxidation of water in the oxygen-evolving complex (OEC of photosystem II (PSII in plants. Despite this essential role of Mn in generating the electrons driving photosynthesis, limited information is available on how Mn deficiency affects PSII functionality. We have here used parameters derived from measurements of fluorescence induction kinetics (OJIP transients, non-photochemical quenching and PSII subunit composition to investigate how latent Mn deficiency changes the photochemistry in two barley genotypes differing in Mn efficiency. Mn deficiency caused dramatic reductions in the quantum yield of PSII and led to the appearance of two new inflection points, the K step and the D dip, in the OJIP fluorescence transients, indicating severe damage to the OEC. In addition, Mn deficiency decreased the ability to induce non-photochemical quenching (NPQ in the light, rendering the plants incapable of dissipating excess energy in a controlled way. Thus, the Mn deficient plants became severely affected in their ability to recover from high light-induced photoinhibition, especially under strong Mn deficiency. Interestingly, the Mn-efficient genotype was able to maintain a higher non-photochemical quenching than the Mn-inefficient genotype when exposed to mild Mn deficiency. However, during severe Mn deficiency, there were no differences between the two genotypes, suggesting a general loss of the ability to disassemble and repair PSII. The pronounced defects of PSII activity were supported by a dramatic decrease in the abundance of the OEC protein subunits, PsbP and PsbQ in response to Mn deficiency for both genotypes. We conclude that regulation of photosynthetic performance by means of maintaining and inducing NPQ mechanisms contribute to genotypic differences in the Mn efficiency of barley genotypes growing under conditions with mild Mn deficiency.

Soft-Body Muscles for Evolved Virtual Creatures: The Next Step on a Bio-Mimetic Path to Meaningful Morphological Complexity

DEFF Research Database (Denmark)

Lessin, Dan; Risi, Sebastian

2015-01-01

In the past, evolved virtual creatures (EVCs) have been developed with rigid, segmented bodies, and with soft bodies, but never before with a combination of the two. In nature, however, creatures combining a rigid skeleton and non-rigid muscles are some of the most complex and successful examples...... of life on earth. Now, for the first time, creatures with fully evolved rigid-body skeletons and soft-body muscles can be developed in the virtual world, as well. By exploiting and re-purposing the capabilities of existing soft-body simulation systems, we can evolve complex and effective simulated muscles...

Water Splitting by Thin Film Metal-Oxo Catalysts

Energy Technology Data Exchange (ETDEWEB)

Nocera, Daniel [Harvard Univ., Cambridge, MA (United States)

2013-03-15

The dropping price of silicon photovoltaics in the United States is causing load defection to solar supply at an accelerated pace. This conversion to solar and, more generally, other renewable energy sources has accordingly turned the energy research focus from generation to one of storage. Truly disruptive improvements in energy storage technologies are limited by energy density. This limitation, however, does not apply to fuels, which possess the energy density needed for large-scale energy storage. The first step of the basic science needed to drive such historic restructuring of the U.S. energy infrastructure begins with the solar-driven generation of hydrogen and oxygen from water. The solar-produced hydrogen may then be combined with carbon dioxide to deliver any number of fuels. Obviously, light does not directly act on water to engender its splitting into its elemental components. Hence, catalysts are needed to drive the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Of these two reactions, the four-electron, four-proton oxidation of OER is the more kinetically challenging reaction, and therefore the development of energy efficient solar fuels processes demands that OER be accomplished at a minimal overpotential. The research completed in this program developed catalysts that drive OER and at the same time meet the important criteria of (1) using non-critical materials that (2) are easy to assemble and (3) accomplish OER under simple conditions. Research was designed to uncover the chemical principles that underlie the self-assembly of metal oxide oxygen evolving catalysts (M-OEC) from the metals of M = Mn, Co, and Ni. For example, a dogma of heterogeneous catalysis of any sort is that “edges” matter in promoting catalytic transformations. We provided a rationale for such dogma by showing that the OER in Co-OEC occurred at a dimensionally reduced dicobalt edge site. Edge site reactivity was clearly revealed analyzing 18O labeled

Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

International Nuclear Information System (INIS)

Nizel'skij, Yu.N.; Ishchenko, S.S.; Lipatova, T.Eh.

1985-01-01

The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr 3+ , VO 2+ , MoOΛ2 2+ , Co 3+ , Mn 3+ , Ni 2+ , Fe 3+ ) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

Radiation accelerated formation of oxygen and carbon related complexes in silicon

International Nuclear Information System (INIS)

Lazrak, A.; Magnea, N.; Pautrat, J.L.

1984-06-01

During the pulling of silicon monocrystals by the Czochralsky method, oxygen is incorporated into the lattice. It is known from early works that low temperature annealings (400-1000 0 C) make this oxygen to precipitate and a number of different defects to be generated. In order to check whether the fast diffusivity of an oxygen silicon interstitial complex has to be taken in consideration it was interesting to examinate the possible role of radiation damage on the formation of oxygen related defects. Experimental results of an experiment are presented and discussed

Changes of Photosynthetic Behaviors in Kappaphycus alvarezii Infected by Epiphyte

Directory of Open Access Journals (Sweden)

Tong Pang

2011-01-01

Full Text Available Epiphytic filamentous algae (EFA were noted as a serious problem to reduce the production and quality of K. alvarezii. The morphological studies revealed that the main epiphyte on K. alvarezii was Neosiphonia savatieri in China. Though the harmful effects of EFA on the production of K. alvarezii have been reported, the detailed mechanism of the N. savatieri in limiting the production of K. alvarezii has not been studied yet. The present paper studied the effects of N. savatieri infection on photosynthetic behaviors in K. alvarezii by detecting chlorophyll fluorescence transient in vivo. The results revealed that damage of oxygen-evolving complex (OEC, decrease of active reaction centers (RCs, and the plastoquinone (PQ pool as well as significant reduction in the performance indexes (PI of PSII were caused by the infection of N. savatieri. The influence of N. savatieri on photosynthetic activity of K. alvarezii should be one of the important reasons to reduce the production of K. alvarezii infected by N. savatieri.

Changes of Photosynthetic Behaviors in Kappaphycus alvarezii Infected by Epiphyte.

Science.gov (United States)

Pang, Tong; Liu, Jianguo; Liu, Qian; Lin, Wei

2011-01-01

Epiphytic filamentous algae (EFA) were noted as a serious problem to reduce the production and quality of K. alvarezii. The morphological studies revealed that the main epiphyte on K. alvarezii was Neosiphonia savatieri in China. Though the harmful effects of EFA on the production of K. alvarezii have been reported, the detailed mechanism of the N. savatieri in limiting the production of K. alvarezii has not been studied yet. The present paper studied the effects of N. savatieri infection on photosynthetic behaviors in K. alvarezii by detecting chlorophyll fluorescence transient in vivo. The results revealed that damage of oxygen-evolving complex (OEC), decrease of active reaction centers (RCs), and the plastoquinone (PQ) pool as well as significant reduction in the performance indexes (PI) of PSII were caused by the infection of N. savatieri. The influence of N. savatieri on photosynthetic activity of K. alvarezii should be one of the important reasons to reduce the production of K. alvarezii infected by N. savatieri.

Efficient carbon dots/NiFe-layered double hydroxide/BiVO4 photoanodes for photoelectrochemical water splitting

Science.gov (United States)

Lv, Xiaowei; Xiao, Xin; Cao, Minglei; Bu, Yi; Wang, Chuanqing; Wang, Mingkui; Shen, Yan

2018-05-01

Modification of semiconductor photoanodes with oxygen evolution catalyst (OEC) is an effective approach for improving photoelectrochemical (PEC) water splitting efficiency. In the configuration, how to increase the activity of OEC is crucial to further improve PEC performance. Herein, a ternary photoanode system was designed to enhance PEC efficiency of photoelectrodes through introducing carbon dots (CDs), NiFe-layered double hydroxide (NiFe-LDH) nanosheets on BiVO4 particles. Systematic research shows that NiFe-LDH serves as an OEC which accelerates oxygen evolution kinetics, while the introduction of CDs can further reduce charge transfer resistance and overpotential for oxygen evolution. Under the synergistic effect of NiFe-LDH and CDs, the photocurrent and incident photon to current conversion efficiency (IPCE) of the resulting CDs/NiFe-LDH/BiVO4 photoanode is improved significantly than those of the NiFe-LDH/BiVO4 electrode. Consequently, such a ternary heterostructure could be an alternative way to further enhance PEC water splitting performance.

Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

Science.gov (United States)

Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

2018-05-04

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

Science.gov (United States)

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Envisioning a New Foundation for Gifted Education: Evolving Complexity Theory (ECT) of Talent Development

Science.gov (United States)

Dai, David Yun

2017-01-01

This article presents a new theory of talent development, evolving complexity theory (ECT), in the context of the changing theoretical directions as well as the landscape of gifted education. I argue that gifted education needs a new foundation that provides a broad psychosocial basis than what the notion of giftedness can afford. A focus on…

Analysis of oxygen-enhanced combustion of gas power cycle

Energy Technology Data Exchange (ETDEWEB)

Maidana, Cristiano Frandalozo; Carotenuto, Adriano; Schneider, Paulo Smith [Universidade Federal do Rio Grande do Sul (GESTE/UFRGS), Porto Alegre, RS (Brazil). Grupo de Estudos Termicos e Energeticos], E-mails: cristiano.maidana@ufrgs.br, pss@mecanica.ufrgs.br

2010-07-01

The majority of combustion processes use air as oxidant, roughly taken as 21% O{sub 2} and 79% N{sub 2}, by volume. In many cases, these processes can be enhanced by using an oxidant that contains higher proportion of O{sub 2} than in air. This is known as oxygen-enhanced combustion or OEC, and can bring important benefits like higher thermal efficiencies, lower exhaust gas volumes, higher heat transfer efficiency, reduction fuel consumption, reduced equipment costs and substantially pollutant emissions reduction. Within this scenario, this paper aims to investigate the influence of 21-30% oxygen concentration on the performance of a air-fired natural gas fueled power plant. This power plant operates under a Brayton cycle with models with the help of an air flow splitter after the compressor output in order to dose the oxygen rate of combustion and to keep the flue gas intake of the turbine at a prescribed temperature. Simulations shows that the enhancing of the oxidant stream reduced fuel consumption of about 10%, driven by higher adiabatic flame temperatures, which improves thermal and heat transfer efficiencies. A conclusion obtained is that the use of oxygen in higher proportions can be a challenge to retrofit existing air-fired natural gas power turbine cycles, because of the technological limitation of its materials with higher flame temperatures. (author)

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

Science.gov (United States)

Franke, David P.; Hoehne, Felix; Vlasenko, Leonid S.; Itoh, Kohei M.; Brandt, Martin S.

2014-05-01

Spin-dependent relaxation and recombination processes in γ-irradiated n-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, the other a charge transfer between 31P donors and SL1 centers forming close pairs, as indicated by electrically detected electron double resonance. For both processes, the recombination dynamics is studied with pulsed EDMR techniques. We demonstrate the feasibility of true zero-field cw and pulsed EDMR for spin-1 systems and use this to measure the lifetimes of the different spin states of SL1 also at vanishing external magnetic field.

A foundational methodology for determining system static complexity using notional lunar oxygen production processes

Science.gov (United States)

Long, Nicholas James

This thesis serves to develop a preliminary foundational methodology for evaluating the static complexity of future lunar oxygen production systems when extensive information is not yet available about the various systems under consideration. Evaluating static complexity, as part of a overall system complexity analysis, is an important consideration in ultimately selecting a process to be used in a lunar base. When system complexity is higher, there is generally an overall increase in risk which could impact the safety of astronauts and the economic performance of the mission. To evaluate static complexity in lunar oxygen production, static complexity is simplified and defined into its essential components. First, three essential dimensions of static complexity are investigated, including interconnective complexity, strength of connections, and complexity in variety. Then a set of methods is developed upon which to separately evaluate each dimension. Q-connectivity analysis is proposed as a means to evaluate interconnective complexity and strength of connections. The law of requisite variety originating from cybernetic theory is suggested to interpret complexity in variety. Secondly, a means to aggregate the results of each analysis is proposed to create holistic measurement for static complexity using the Single Multi-Attribute Ranking Technique (SMART). Each method of static complexity analysis and the aggregation technique is demonstrated using notional data for four lunar oxygen production processes.

Carotenoid-protein complexes and their stability towards oxygen and radiation

International Nuclear Information System (INIS)

Ramakrishnan, T.V.; Francis, F.J.

1980-01-01

Carotenoid-protein complexes isolated from fresh mangoes were found to be more stable to oxygen and radiation when dissolved in water as compared with β-carotene in petroleum ether. Part of the pigment could be released from the complex by gamma irradiation. Observations on the stability of the carotenoid (98% β-carotene) in the complex indicated that the pigment is either associated with the lipid prosthetic group of the protein or loosely attached to the protein by weak hydrophobic bonds. (author)

Electrospinning fabrication and oxygen sensing properties of Cu(I) complex-polystyrene composite microfibrous membranes

Energy Technology Data Exchange (ETDEWEB)

Wang Liyan, E-mail: wanglykmmc@163.co [Department of Orthodontics, School of Stomatology, Fourth Military Medical University, XiAn (China); Xu Yun [Department of Orthodontics, School of Stomatology, KunMing Medical College, Kunming (China); Lin Zhu [Department of Orthodontics, School of Stomatology, Fourth Military Medical University, XiAn (China); Zhao Ning [Department of Orthodontics, School of Stomatology, West China College, SiChuan University, ChengDu (China); Xu Yanhua [Department of Orthodontics, School of Stomatology, KunMing Medical College, Kunming (China)

2011-07-15

In this paper, a phosphorescent Cu(I) complex of [Cu(POP)(ECI-Phen)]BF{sub 4}, where POP=bis[2-(diphenylphosphino)phenyl]ether, and ECI-Phen=1-ethyl-2-(N-ethyl-carbazole-yl-4-)imidazo[4,5-f]1,10-phenanthroline, is incorporated into a polystyrene matrix of polystyrene (PS) to form microfibers membranes. The possibility of using the resulted composite microfibrous membranes as an optical oxygen sensor is explored. Good linearity and short response time are obtained with a sensitivity of 9.8. These results suggest that phosphorescent [Cu(POP)(ECI-Phen)]BF{sub 4} is a promising candidate for oxygen-sensors and PS is an excellent matrix for oxygen sensing material because it owns a large surface-area-to-volume ratio and can supply a homogeneous matrix for probe molecules. Further analysis suggests that the molecular structure of diamine ligand in Cu(I) complexes is critical for sensitivity due to the characteristic electronic structure of excited state Cu(I) complexes. - Highlights: {yields} Cu(I) complex is incorporated into polystyrene matrix to form nanofibers. {yields} Resulted sample exhibit good linearity and short response time. {yields} PS is an excellent matrix for oxygen sensing material for probe molecules. {yields} Molecular structure of diamine ligand is critical for sensitivity.

Electrospinning fabrication and oxygen sensing properties of Cu(I) complex-polystyrene composite microfibrous membranes

International Nuclear Information System (INIS)

Wang Liyan; Xu Yun; Lin Zhu; Zhao Ning; Xu Yanhua

2011-01-01

In this paper, a phosphorescent Cu(I) complex of [Cu(POP)(ECI-Phen)]BF 4 , where POP=bis[2-(diphenylphosphino)phenyl]ether, and ECI-Phen=1-ethyl-2-(N-ethyl-carbazole-yl-4-)imidazo[4,5-f] 1,10-phenanthroline, is incorporated into a polystyrene matrix of polystyrene (PS) to form microfibers membranes. The possibility of using the resulted composite microfibrous membranes as an optical oxygen sensor is explored. Good linearity and short response time are obtained with a sensitivity of 9.8. These results suggest that phosphorescent [Cu(POP)(ECI-Phen)]BF 4 is a promising candidate for oxygen-sensors and PS is an excellent matrix for oxygen sensing material because it owns a large surface-area-to-volume ratio and can supply a homogeneous matrix for probe molecules. Further analysis suggests that the molecular structure of diamine ligand in Cu(I) complexes is critical for sensitivity due to the characteristic electronic structure of excited state Cu(I) complexes. - Highlights: → Cu(I) complex is incorporated into polystyrene matrix to form nanofibers. → Resulted sample exhibit good linearity and short response time. → PS is an excellent matrix for oxygen sensing material for probe molecules. → Molecular structure of diamine ligand is critical for sensitivity.

Biogeochemistry: Oxygen burrowed away

NARCIS (Netherlands)

Meysman, F.J.R.

2014-01-01

Multicellular animals probably evolved at the seafloor after a rise in oceanic oxygen levels. Biogeochemical model simulations suggest that as these animals started to rework the seafloor, they triggered a negative feedback that reduced global oxygen.

The effect of carbon and boron on the accumulation of vacancy-oxygen complexes in silicon

International Nuclear Information System (INIS)

Akhmetov, V.D.; Bolotov, V.V.

1980-01-01

By means of IR-absorption measurements the dose dependencies of the concentrations of vacancy-oxygen complexes (VO), interstitial oxygen atoms (Osub(I)), substitutional carbon atoms (Csub(S)) and interstitial carbon-oxygen complexes (Csub(I)Osub(I)) in n- and p-type silicon irradiated with 1.1 MeV electrons have been investigated. The observed increase of the production rate of VO-complexes with the rise of carbon and boron atoms concentrations (these impurities act as sinks for silicon interstitial atoms) has been explained in terms of annihilation of the vacancies and interstitials on the oxygen atoms. The results obtained show that boron atoms are more effective sinks than carbon atoms for the interstitial silicon atoms. That seems to be connected not only with the higher probability of boron injection into interstitial position but also with the further capture of interstitial silicon atoms on the interstitial boron, i.e. with the interstitial cluster formation. (author)

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

Science.gov (United States)

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.

Proterozoic atmospheric oxygen

DEFF Research Database (Denmark)

Canfield, Donald Eugene

2014-01-01

This article is concerned with the evolution of atmospheric oxygen concentrations through the Proterozoic Eon. In particular, this article will seek to place the history of atmospheric oxygenation through the Proterozoic Eon in the context of the evolving physical environment including the history...... of continental growth and volcanic outgassing, as well as biogeochemical processing of elements within the oceans. The author will seek to explore constraints on the history of oxygenation and understand which processes have regulated oxygen through this eon....

A neighbourhood evolving network model

International Nuclear Information System (INIS)

Cao, Y.J.; Wang, G.Z.; Jiang, Q.Y.; Han, Z.X.

2006-01-01

Many social, technological, biological and economical systems are best described by evolved network models. In this short Letter, we propose and study a new evolving network model. The model is based on the new concept of neighbourhood connectivity, which exists in many physical complex networks. The statistical properties and dynamics of the proposed model is analytically studied and compared with those of Barabasi-Albert scale-free model. Numerical simulations indicate that this network model yields a transition between power-law and exponential scaling, while the Barabasi-Albert scale-free model is only one of its special (limiting) cases. Particularly, this model can be used to enhance the evolving mechanism of complex networks in the real world, such as some social networks development

PHOTOINDUCED TRANSFER OF OXYGEN FROM WATER: AN ARTIFICAL PHOTOSYNTHETIC SYSTEM

Energy Technology Data Exchange (ETDEWEB)

Willner, Itamar; Otvos, John W.; Ford, William E.; Mettee, Howard; Calvin, Melvin

1979-11-01

The photoinduced splitting of water into hydrogen and oxygen has evoked great interest in recent years as a means for energy storag eand fuel production. Photoinduced reduction of water to hydrogen, using visible light, has been described using heterogeneous or homogeneous catalysts. However, the complementary part involving the oxidation of water to oxygen is required in order to create a cyclic artificial 'photosynthetic' fuel system. The major difficulty assocaited with the photooxidation of water involves the requirement for a four electron transfer to produce oxygen. A stepwise one-electron oxidation of water is unfavorable due to the implied formation of active hydroxyl radicals. Very recently, it has been reported that RuO{sub 2} can serve as a heterogeneous charge storage catalyst for oxygen production. On the basis of the limited knowledge about natural photosynthesis, in which manganese ions play an important role in oxygen evolution, synthetic manganese complexes, and in particular dimeric complexes, have been proposed as potential catalysts for oxygen production. So far, efforts directed toward this goal have been unsuccessful. Consequently, using a manganese complex, they attempted to perform a photoinduced oxidation of water whereby the active oxygen is transferred to a trapping substrate. In such a way, the requirement for a dimerization process to evolve molecular oxygen is avoided. They wish to report a photoinduced redox cycle sensitized by a manganese porphyrin, 5-(4{prime}-hexadecylpyridium)-10, 15, 20-tri (4{prime}-pyridyl)-porphinatomanganese(III) (abbreciated to Pn-Mn{sup III}) in which the resultant reaction is the oxidation of water and trapping of the single oxygen atom by a substrate (triphenylphosphine).

The Complex Transcriptional Response of Acaryochloris marina to Different Oxygen Levels

Directory of Open Access Journals (Sweden)

Miguel A. Hernández-Prieto

2017-02-01

Full Text Available Ancient oxygenic photosynthetic prokaryotes produced oxygen as a waste product, but existed for a long time under an oxygen-free (anoxic atmosphere, before an oxic atmosphere emerged. The change in oxygen levels in the atmosphere influenced the chemistry and structure of many enzymes that contained prosthetic groups that were inactivated by oxygen. In the genome of Acaryochloris marina, multiple gene copies exist for proteins that are normally encoded by a single gene copy in other cyanobacteria. Using high throughput RNA sequencing to profile transcriptome responses from cells grown under microoxic and hyperoxic conditions, we detected 8446 transcripts out of the 8462 annotated genes in the Cyanobase database. Two-thirds of the 50 most abundant transcripts are key proteins in photosynthesis. Microoxic conditions negatively affected the levels of expression of genes encoding photosynthetic complexes, with the exception of some subunits. In addition to the known regulation of the multiple copies of psbA, we detected a similar transcriptional pattern for psbJ and psbU, which might play a key role in the altered components of photosystem II. Furthermore, regulation of genes encoding proteins important for reactive oxygen species-scavenging is discussed at genome level, including, for the first time, specific small RNAs having possible regulatory roles under varying oxygen levels.

The Complex Transcriptional Response of Acaryochloris marina to Different Oxygen Levels

Science.gov (United States)

Hernández-Prieto, Miguel A.; Lin, Yuankui; Chen, Min

2016-01-01

Ancient oxygenic photosynthetic prokaryotes produced oxygen as a waste product, but existed for a long time under an oxygen-free (anoxic) atmosphere, before an oxic atmosphere emerged. The change in oxygen levels in the atmosphere influenced the chemistry and structure of many enzymes that contained prosthetic groups that were inactivated by oxygen. In the genome of Acaryochloris marina, multiple gene copies exist for proteins that are normally encoded by a single gene copy in other cyanobacteria. Using high throughput RNA sequencing to profile transcriptome responses from cells grown under microoxic and hyperoxic conditions, we detected 8446 transcripts out of the 8462 annotated genes in the Cyanobase database. Two-thirds of the 50 most abundant transcripts are key proteins in photosynthesis. Microoxic conditions negatively affected the levels of expression of genes encoding photosynthetic complexes, with the exception of some subunits. In addition to the known regulation of the multiple copies of psbA, we detected a similar transcriptional pattern for psbJ and psbU, which might play a key role in the altered components of photosystem II. Furthermore, regulation of genes encoding proteins important for reactive oxygen species-scavenging is discussed at genome level, including, for the first time, specific small RNAs having possible regulatory roles under varying oxygen levels. PMID:27974439

Study of the Mn-binding sites in photosystem II using antibodies raised against lumenal regions of the D1 and D2 reaction center proteins

Energy Technology Data Exchange (ETDEWEB)

Dalmasso, Enrique Agustin [Univ. of California, Berkeley, CA (United States)

1992-04-01

The experiments discussed in this thesis focus on identifying the protein segments or specific amino acids which provide ligands to the Mn cluster of photosystem II (PS II). This Mn cluster plays a central role in the oxygen-evolving complex (OEC) of PS II. The Mn cluster is thought to be bound by lumenal regions of the PS II reaction center proteins known as D1 and D2. First, several peptides were synthesized which correspond to specific lumenal segments of the D1 and D2 proteins. Next, polyclonal antibodies were successfully elicited using three of these peptides. The peptides recognized by these antibodies correspond to protein segments of the spinach reaction center proteins: Ile-321 to Ala-344 of D1 (D1-a), Asp-319 to Arg-334 of D1 (D1-b), and Val-300 to Asn-319 of D2 (D2-a). These antibodies were then used in assays which were developed to structurally or functionally probe the potential Mn-binding regions of the D1 and D2 proteins.

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.

Science.gov (United States)

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.

Luminescent Oxygen Gas Sensors Based on Nanometer-Thick Hybrid Films of Iridium Complexes and Clay Minerals

Directory of Open Access Journals (Sweden)

Hisako Sato

2014-01-01

Full Text Available The use of Ir(III complexes in photo-responsive molecular devices for oxygen gas sensing is reviewed. Attention is focused on the immobilization of Ir(III complexes in organic or inorganic host materials such as polymers, silica and clays in order to enhance robustness and reliability. Our recent works on constructing nanometer-thick films comprised of cyclometalated cationic Ir(III complexes and clay minerals are described. The achievement of multi-emitting properties in response to oxygen pressure is demonstrated.

Oxygen and oxidative stress in the perinatal period

Directory of Open Access Journals (Sweden)

Isabel Torres-Cuevas

2017-08-01

Full Text Available 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

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

International Nuclear Information System (INIS)

Thronson, H.A. Jr.; Latter, W.B.; Black, J.H.; Bally, J.; Hacking, P.; Steward Observatory, Tucson, AZ; AT and T Bell Laboratories, Holmdel, NJ; Cornell Univ., Ithaca, NY; California Institute of Technology, Pasadena)

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. 53 references

Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.

Science.gov (United States)

Van Allsburg, Kurt M; Anzenberg, Eitan; Drisdell, Walter S; Yano, Junko; Tilley, T Don

2015-03-16

[Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4 cubane complex combining the structural inspiration of the photosystem II oxygen-evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen-atom acceptor (PEt3), to give the butterfly complex [Mn4O2{O2P(OtBu)2}6(OPEt3)2]. The cubane structure is restored by reaction of the latter complex with the O-atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X-ray absorption spectroscopy to determine the fate of the Mn4O4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn(II) species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin = pinacolate) is described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The genotype-phenotype map of an evolving digital organism.

Directory of Open Access Journals (Sweden)

Miguel A Fortuna

2017-02-01

Full Text Available To understand how evolving systems bring forth novel and useful phenotypes, it is essential to understand the relationship between genotypic and phenotypic change. Artificial evolving systems can help us understand whether the genotype-phenotype maps of natural evolving systems are highly unusual, and it may help create evolvable artificial systems. Here we characterize the genotype-phenotype map of digital organisms in Avida, a platform for digital evolution. We consider digital organisms from a vast space of 10141 genotypes (instruction sequences, which can form 512 different phenotypes. These phenotypes are distinguished by different Boolean logic functions they can compute, as well as by the complexity of these functions. We observe several properties with parallels in natural systems, such as connected genotype networks and asymmetric phenotypic transitions. The likely common cause is robustness to genotypic change. We describe an intriguing tension between phenotypic complexity and evolvability that may have implications for biological evolution. On the one hand, genotypic change is more likely to yield novel phenotypes in more complex organisms. On the other hand, the total number of novel phenotypes reachable through genotypic change is highest for organisms with simple phenotypes. Artificial evolving systems can help us study aspects of biological evolvability that are not accessible in vastly more complex natural systems. They can also help identify properties, such as robustness, that are required for both human-designed artificial systems and synthetic biological systems to be evolvable.

The genotype-phenotype map of an evolving digital organism.

Science.gov (United States)

Fortuna, Miguel A; Zaman, Luis; Ofria, Charles; Wagner, Andreas

2017-02-01

To understand how evolving systems bring forth novel and useful phenotypes, it is essential to understand the relationship between genotypic and phenotypic change. Artificial evolving systems can help us understand whether the genotype-phenotype maps of natural evolving systems are highly unusual, and it may help create evolvable artificial systems. Here we characterize the genotype-phenotype map of digital organisms in Avida, a platform for digital evolution. We consider digital organisms from a vast space of 10141 genotypes (instruction sequences), which can form 512 different phenotypes. These phenotypes are distinguished by different Boolean logic functions they can compute, as well as by the complexity of these functions. We observe several properties with parallels in natural systems, such as connected genotype networks and asymmetric phenotypic transitions. The likely common cause is robustness to genotypic change. We describe an intriguing tension between phenotypic complexity and evolvability that may have implications for biological evolution. On the one hand, genotypic change is more likely to yield novel phenotypes in more complex organisms. On the other hand, the total number of novel phenotypes reachable through genotypic change is highest for organisms with simple phenotypes. Artificial evolving systems can help us study aspects of biological evolvability that are not accessible in vastly more complex natural systems. They can also help identify properties, such as robustness, that are required for both human-designed artificial systems and synthetic biological systems to be evolvable.

Oxygen and oxidative stress in the perinatal period.

Science.gov (United States)

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

Oxygenation of the Mesoproterozoic ocean and the evolution of complex eukaryotes

Science.gov (United States)

Zhang, Kan; Zhu, Xiangkun; Wood, Rachel A.; Shi, Yao; Gao, Zhaofu; Poulton, Simon W.

2018-05-01

The Mesoproterozoic era (1,600-1,000 million years ago (Ma)) has long been considered a period of relative environmental stasis, with persistently low levels of atmospheric oxygen. There remains much uncertainty, however, over the evolution of ocean chemistry during this period, which may have been of profound significance for the early evolution of eukaryotic life. Here we present rare earth element, iron-speciation and inorganic carbon isotope data to investigate the redox evolution of the 1,600-1,550 Ma Yanliao Basin, North China Craton. These data confirm that the ocean at the start of the Mesoproterozoic was dominantly anoxic and ferruginous. Significantly, however, we find evidence for a progressive oxygenation event starting at 1,570 Ma, immediately prior to the occurrence of complex multicellular eukaryotes in shelf areas of the Yanliao Basin. Our study thus demonstrates that oxygenation of the Mesoproterozoic environment was far more dynamic and intense than previously envisaged, and establishes an important link between rising oxygen and the emerging record of diverse, multicellular eukaryotic life in the early Mesoproterozoic.

Microencapsulation improves inhibitory effects of transplanted olfactory ensheathing cells on pain after sciatic nerve injury

Directory of Open Access Journals (Sweden)

Hao Zhao

2015-01-01

Full Text Available Olfactory bulb tissue transplantation inhibits P2X2/3 receptor-mediated neuropathic pain. However, the olfactory bulb has a complex cellular composition, and the mechanism underlying the action of purified transplanted olfactory ensheathing cells (OECs remains unclear. In the present study, we microencapsulated OECs in alginic acid, and transplanted free and microencapsulated OECs into the region surrounding the injured sciatic nerve in rat models of chronic constriction injury. We assessed mechanical nociception in the rat models 7 and 14 days after surgery by measuring paw withdrawal threshold, and examined P2X2/3 receptor expression in L 4-5 dorsal root ganglia using immunohistochemistry. Rats that received free and microencapsulated OEC transplants showed greater withdrawal thresholds than untreated model rats, and weaker P2X2/3 receptor immunoreactivity in dorsal root ganglia. At 14 days, paw withdrawal threshold was much higher in the microencapsulated OEC-treated animals. Our results confirm that microencapsulated OEC transplantation suppresses P2X2/3 receptor expression in L 4-5 dorsal root ganglia in rat models of neuropathic pain and reduces allodynia, and also suggest that transplantation of microencapsulated OECs is more effective than transplantation of free OECs for the treatment of neuropathic pain.

Forward current enhanced elimination of the radiation induced boron-oxygen complex in silicon n+-p diodes

CERN Document Server

Makarenko, L F; Yakushevich, H S; Moll, M; Pintilie, I

2014-01-01

Using forward current injection with densities in the range 15-30A/cm(2) we can effectively eliminate the radiation-induced boron-oxygen complex, which is the main compensating center in irradiated Si solar cells. It was found that for a given forward current density the elimination rate is decreasing with increasing irradiation dose. Additionally, some evidences have been obtained on the negative-U properties of the radiation-induced boron-oxygen complex.

Formation and annealing of metastable (interstitial oxygen)-(interstitial carbon) complexes in n- and p-type silicon

CERN Document Server

Makarenko, L F; Lastovskii, S B; Murin, L I; Moll, M; Pintilie, I

2014-01-01

It is shown experimentally that, in contrast to the stable configuration of (interstitial carbon)-(interstitial oxygen) complexes (CiOi), the corresponding metastable configuration (CiOi{*}) cannot be found in n-Si based structures by the method of capacitance spectroscopy. The rates of transformation CiOi{*} -> CiOi are practically the same for both n- and p-Si with a concentration of charge carriers of no higher than 10(13) cm(-3). It is established that the probabilities of the simultaneous formation of stable and metastable configurations of the complex under study in the case of the addition of an atom of interstitial carbon to an atom of interstitial oxygen is close to 50\\%. This is caused by the orientation dependence of the interaction potential of an atom of interstitial oxygen with an interstitial carbon atom, which diffuses to this oxygen atom.

3d-4f {Co(II)3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts.

Science.gov (United States)

Evangelisti, Fabio; Moré, René; Hodel, Florian; Luber, Sandra; Patzke, Greta Ricarda

2015-09-02

Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [Co(II)3Ln(hmp)4(OAc)5H2O] ({Co(II)3Ln(OR)4}; Ln = Ho-Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {Co(II)3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln(3+) centers as redox-inactive Ca(2+) analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s(-1)). Furthermore, they open up the important family of 3d-4f complexes for photocatalytic applications. The stability of the {Co(II)3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln(3+) centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born-Oppenheimer molecular dynamics studies.

A rhenium complex doped in a silica molecular sieve for molecular oxygen sensing: Construction and characterization.

Science.gov (United States)

Yang, Xiaozhou; Li, Yanxiao

2016-01-15

This paper reported a diamine ligand and its Re(I) complex for potential application in oxygen sensing. The novelty of this diamine ligand localized at its increased conjugation chain which had a typical electron-withdrawing group of 1,3,4-oxadiazole. Electronic distribution of excited electrons and their lifetime were supposed to be increased, favoring oxygen sensing collision. This hypothesis was confirmed by single crystal analysis, theoretical calculation and photophysical measurement. It was found that this Re(I) complex had a long-lived emission peaking at 545 nm, favoring sensing application. By doping this complex into a silica matrix MCM-41, oxygen sensing performance and mechanism of the resulting composites were discussed in detail. Non-linear Stern-Volmer working curves were observed with maximum sensitivity of 5.54 and short response time of ~6 s. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanism of interaction of Al3+ with the proteins composition of photosystem II.

Directory of Open Access Journals (Sweden)

Imed Hasni

Full Text Available The inhibitory effect of Al3+on photosystem II (PSII electron transport was investigated using several biophysical and biochemical techniques such as oxygen evolution, chlorophyll fluorescence induction and emission, SDS-polyacrylamide and native green gel electrophoresis, and FTIR spectroscopy. In order to understand the mechanism of its inhibitory action, we have analyzed the interaction of this toxic cation with proteins subunits of PSII submembrane fractions isolated from spinach. Our results show that Al 3+, especially above 3 mM, strongly inhibits oxygen evolution and affects the advancement of the S states of the Mn4O5Ca cluster. This inhibition was due to the release of the extrinsic polypeptides and the disorganization of the Mn4O5Ca cluster associated with the oxygen evolving complex (OEC of PSII. This fact was accompanied by a significant decline of maximum quantum yield of PSII (Fv/Fm together with a strong damping of the chlorophyll a fluorescence induction. The energy transfer from light harvesting antenna to reaction centers of PSII was impaired following the alteration of the light harvesting complex of photosystem II (LHCII. The latter result was revealed by the drop of chlorophyll fluorescence emission spectra at low temperature (77 K, increase of F0 and confirmed by the native green gel electrophoresis. FTIR measurements indicated that the interaction of Al 3+ with the intrinsic and extrinsic polypeptides of PSII induces major alterations of the protein secondary structure leading to conformational changes. This was reflected by a major reduction of α-helix with an increase of β-sheet and random coil structures in Al 3+-PSII complexes. These structural changes are closely related with the functional alteration of PSII activity revealed by the inhibition of the electron transport chain of PSII.

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

Science.gov (United States)

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.

[Generation of Superoxide Radicals by Complex III in Heart Mitochondria and Antioxidant Effect of Dinitrosyl Iron Complexes at Different Partial Pressure of Oxygen].

Science.gov (United States)

Dudylina, A L; Ivanova, M V; Shumaev, K B; Ruuge, E K

2016-01-01

The EPR spin-trapping technique and EPR-oximetry were used to study generation of superoxide radicals in heart mitochondria isolated from Wistar rats under conditions of variable oxygen concentration. Lithium phthalocyanine and TEMPONE-15N-D16 were chosen to determine oxygen content in a gas-permeable capillary tube containing mitochondria. TIRON was used as a spin trap. We investigated the influence of different oxygen concentrations in incubation mixture and demonstrated that heart mitochondria can generate superoxide in complex III at different partial pressure of oxygen as well as under the conditions of deep hypoxia (partial pressure of oxygen, but the magnitude and kinetic characteristics of the effect depended on the concentration of the drug.

Optical oxygen sensing materials based on a novel dirhenium(I) complex assembled in mesoporous silica

International Nuclear Information System (INIS)

Liu Yanhong; Li Bin; Cong Yan; Zhang Liming; Fan Di; Shi Linfang

2011-01-01

A new dirhenium(I) complex fac-[{Re(CO) 3 (4,7-dinonadecyl-1,10-phenanthro -line)} 2 (4,4'-bipyridyl)] (trifluoromethanesulfonate) 2 (denoted as D-Re(I) ) is assembled in MCM-41 and SBA-15 type mesoporous silica support. The emission peaks of D-Re(I) in D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are observed at 522 and 517 nm, respectively. Their long excited lifetimes, which are of the order of microseconds, indicate the presence of phosphorescence emission arising from the metal to ligand charge-transfer (MLCT) transition. The luminescence intensities of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 decrease remarkably with increase in the oxygen concentration, meaning that they can be used as optical oxygen sensing materials based on luminescence quenching. The ratios I 0 /I 100 of D-Re(I)/MCM-41 and D-Re(I)/SBA-15 are estimated to be 5.6 and 20.1, respectively. The obtained Stern-Volmer oxygen quenching plots of the mesoporous sensing materials could be fitted well to the two-site Demas model and Lehrer model. - Research highlights: → Dirhenium(I) complex assembled in mesoporous molecular sieves for oxygen sensor design. → Large α-diimine ligand L used to improve oxygen sensing properties. → High sensitivity (I 0 /I 100 ) up to 20.1.

Adaptation and heterogeneity of Escherichia coli MC1000 growing in complex environments

DEFF Research Database (Denmark)

Puentes-Téllez, Pilar; Hansen, Martin Asser; Sørensen, Søren

2013-01-01

In a study aiming to assess bacterial evolution in complex growth media, we evaluated the long-term adaptive response of Escherichia coli MC1000 in Luria-Bertani (LB) medium. Seven parallel populations were founded and followed over 150 days in sequential batch cultures under three different oxygen...... conditions (defined environments), and 19 evolved forms were isolated. The emergence of forms with enhanced fitness was evident in competition experiments of all evolved forms versus the ancestral strain. The evolved forms were then subjected to phenotypic and genomic analyses relative to the ancestor...... in galR, a repressor of the galactose operon. Concomitantly, the new forms revealed enhanced growth on galactose as well as galactose-containing disaccharides. This response was likely driven by the LB medium....

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

Science.gov (United States)

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.

Light-induced oxidative stress, N-formylkynurenine, and oxygenic photosynthesis.

Directory of Open Access Journals (Sweden)

Tina M Dreaden Kasson

Full Text Available Light stress in plants results in damage to the water oxidizing reaction center, photosystem II (PSII. Redox signaling, through oxidative modification of amino acid side chains, has been proposed to participate in this process, but the oxidative signals have not yet been identified. Previously, we described an oxidative modification, N-formylkynurenine (NFK, of W365 in the CP43 subunit. The yield of this modification increases under light stress conditions, in parallel with the decrease in oxygen evolving activity. In this work, we show that this modification, NFK365-CP43, is present in thylakoid membranes and may be formed by reactive oxygen species produced at the Mn(4CaO(5 cluster in the oxygen-evolving complex. NFK accumulation correlates with the extent of photoinhibition in PSII and thylakoid membranes. A modest increase in ionic strength inhibits NFK365-CP43 formation, and leads to accumulation of a new, light-induced NFK modification (NFK317 in the D1 polypeptide. Western analysis shows that D1 degradation and oligomerization occur under both sets of conditions. The NFK modifications in CP43 and D1 are found 17 and 14 Angstrom from the Mn(4CaO(5 cluster, respectively. Based on these results, we propose that NFK is an oxidative modification that signals for damage and repair in PSII. The data suggest a two pathway model for light stress responses. These pathways involve differential, specific, oxidative modification of the CP43 or D1 polypeptides.

Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

Science.gov (United States)

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

Benefits of Mars ISRU Regolith Water Processing: A Case Study for the NASA Evolvable Mars Campaign

Science.gov (United States)

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

The chemistry in circumstellar envelopes of evolved stars: following the origin of the elements to the origin of life.

Science.gov (United States)

Ziurys, Lucy M

2006-08-15

Mass loss from evolved stars results in the formation of unusual chemical laboratories: circumstellar envelopes. Such envelopes are found around carbon- and oxygen-rich asymptotic giant branch stars and red supergiants. As the gaseous material of the envelope flows from the star, the resulting temperature and density gradients create a complex chemical environment involving hot, thermodynamically controlled synthesis, molecule "freeze-out," shock-initiated reactions, and photochemistry governed by radical mechanisms. In the circumstellar envelope of the carbon-rich star IRC+10216, >50 different chemical compounds have been identified, including such exotic species as C(8)H, C(3)S, SiC(3), and AlNC. The chemistry here is dominated by molecules containing long carbon chains, silicon, and metals such as magnesium, sodium, and aluminum, which makes it quite distinct from that found in molecular clouds. The molecular composition of the oxygen-rich counterparts is not nearly as well explored, although recent studies of VY Canis Majoris have resulted in the identification of HCO(+), SO(2), and even NaCl in this object, suggesting chemical complexity here as well. As these envelopes evolve into planetary nebulae with a hot, exposed central star, synthesis of molecular ions becomes important, as indicated by studies of NGC 7027. Numerous species such as HCO(+), HCN, and CCH are found in old planetary nebulae such as the Helix. This "survivor" molecular material may be linked to the variety of compounds found recently in diffuse clouds. Organic molecules in dense interstellar clouds may ultimately be traced back to carbon-rich fragments originally formed in circumstellar shells.

Diiridium Bimetallic Complexes Function as a Redox Switch To Directly Split Carbonate into Carbon Monoxide and Oxygen.

Science.gov (United States)

Chen, Tsun-Ren; Wu, Fang-Siou; Lee, Hsiu-Pen; Chen, Kelvin H-C

2016-03-23

A pair of diiridium bimetallic complexes exhibit a special type of oxidation-reduction reaction that could directly split carbonate into carbon monoxide and molecular oxygen via a low-energy pathway needing no sacrificial reagent. One of the bimetallic complexes, Ir(III)(μ-Cl)2Ir(III), can catch carbonato group from carbonate and reduce it to CO. The second complex, the rare bimetallic complex Ir(IV)(μ-oxo)2Ir(IV), can react with chlorine to release O2 by the oxidation of oxygen ions with synergistic oxidative effect of iridium ions and chlorine atoms. The activation energy needed for the key reaction is quite low (∼20 kJ/mol), which is far less than the dissociation energy of the C═O bond in CO2 (∼750 kJ/mol). These diiridium bimetallic complexes could be applied as a redox switch to split carbonate or combined with well-known processes in the chemical industry to build up a catalytic system to directly split CO2 into CO and O2.

Determination of nonmetallic elements in actinide complexes by oxygen flask combustion (OFC) (Part 2). Sulphur

International Nuclear Information System (INIS)

Ruikar, P.B.; Nagar, M.S.; Subramanian, M.S.

1989-01-01

This report describes the determination of sulphur in metallic complexes by oxygen flask combustion followed by conductivity titration with standard barium acetate solution in alcoholic medium and lead electrode titration using a lead ion sensitive electrode. Various organic ligands and uranyl and plutonyl synergistic complexes have been analysed by both these methods and the precision and accuracy of the results have been found to be satisfactory. (author). 12 refs., 12 tabs

EVOLVE

CERN Document Server

Deutz, André; Schütze, Oliver; Legrand, Pierrick; Tantar, Emilia; Tantar, Alexandru-Adrian

2017-01-01

This book comprises nine selected works on numerical and computational methods for solving multiobjective optimization, game theory, and machine learning problems. It provides extended versions of selected papers from various fields of science such as computer science, mathematics and engineering that were presented at EVOLVE 2013 held in July 2013 at Leiden University in the Netherlands. The internationally peer-reviewed papers include original work on important topics in both theory and applications, such as the role of diversity in optimization, statistical approaches to combinatorial optimization, computational game theory, and cell mapping techniques for numerical landscape exploration. Applications focus on aspects including robustness, handling multiple objectives, and complex search spaces in engineering design and computational biology.

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

Science.gov (United States)

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.

Computational Genetic Regulatory Networks Evolvable, Self-organizing Systems

CERN Document Server

Knabe, Johannes F

2013-01-01

Genetic Regulatory Networks (GRNs) in biological organisms are primary engines for cells to enact their engagements with environments, via incessant, continually active coupling. In differentiated multicellular organisms, tremendous complexity has arisen in the course of evolution of life on earth. Engineering and science have so far achieved no working system that can compare with this complexity, depth and scope of organization. Abstracting the dynamics of genetic regulatory control to a computational framework in which artificial GRNs in artificial simulated cells differentiate while connected in a changing topology, it is possible to apply Darwinian evolution in silico to study the capacity of such developmental/differentiated GRNs to evolve. In this volume an evolutionary GRN paradigm is investigated for its evolvability and robustness in models of biological clocks, in simple differentiated multicellularity, and in evolving artificial developing 'organisms' which grow and express an ontogeny starting fr...

Rapid Quadrupole-Time-of-Flight Mass Spectrometry Method Quantifies Oxygen-Rich Lignin Compound in Complex Mixtures

Science.gov (United States)

Boes, Kelsey S.; Roberts, Michael S.; Vinueza, Nelson R.

2018-03-01

Complex mixture analysis is a costly and time-consuming task facing researchers with foci as varied as food science and fuel analysis. When faced with the task of quantifying oxygen-rich bio-oil molecules in a complex diesel mixture, we asked whether complex mixtures could be qualitatively and quantitatively analyzed on a single mass spectrometer with mid-range resolving power without the use of lengthy separations. To answer this question, we developed and evaluated a quantitation method that eliminated chromatography steps and expanded the use of quadrupole-time-of-flight mass spectrometry from primarily qualitative to quantitative as well. To account for mixture complexity, the method employed an ionization dopant, targeted tandem mass spectrometry, and an internal standard. This combination of three techniques achieved reliable quantitation of oxygen-rich eugenol in diesel from 300 to 2500 ng/mL with sufficient linearity (R2 = 0.97 ± 0.01) and excellent accuracy (percent error = 0% ± 5). To understand the limitations of the method, it was compared to quantitation attained on a triple quadrupole mass spectrometer, the gold standard for quantitation. The triple quadrupole quantified eugenol from 50 to 2500 ng/mL with stronger linearity (R2 = 0.996 ± 0.003) than the quadrupole-time-of-flight and comparable accuracy (percent error = 4% ± 5). This demonstrates that a quadrupole-time-of-flight can be used for not only qualitative analysis but also targeted quantitation of oxygen-rich lignin molecules in complex mixtures without extensive sample preparation. The rapid and cost-effective method presented here offers new possibilities for bio-oil research, including: (1) allowing for bio-oil studies that demand repetitive analysis as process parameters are changed and (2) making this research accessible to more laboratories. [Figure not available: see fulltext.

Cumulative impacts of an evolving oil-field complex on the distribution of calving caribou

International Nuclear Information System (INIS)

Nellemann, C.; Cameron, R.D.

1998-01-01

A study was conducted to examine the relationship between caribou density and road density as one means of assessing the reaction of caribou to activities associated with the evolving Prudhoe Bay oil-field complex in Alaska. Aerial surveys from 1987 to 1992 have shown that caribou density is inversely related to road density. The effects of avoidance were most apparent in preferred rugged terrain which are important habitats for foraging during the calving period. Female calves were found to be much more sensitive to surface development than adult males and yearlings. The biggest disturbances were caused by initial road construction and related facilities. The recent displacement of some calving activity within the Kuparuk Development area may result in heightened competition for forage, increased risk of predation, and lower productivity of the herd. 43 refs., 3 tabs., 3 figs

Enhanced reactive oxygen species through direct copper sulfide nanoparticle-doxorubicin complexation

Science.gov (United States)

Li, Yajuan; Cupo, Michela; Guo, Liangran; Scott, Julie; Chen, Yi-Tzai; Yan, Bingfang; Lu, Wei

2017-12-01

CuS-based nanostructures loading the chemotherapeutic agent doxorubicin (DOX) exerted excellent cancer photothermal chemotherapy under multi-external stimuli. The DOX loading was generally designed through electrostatic interaction or chemical linkers. However, the interaction between DOX molecules and CuS nanoparticles has not been investigated. In this work, we use PEGylated hollow copper sulfide nanoparticles (HCuSNPs) to directly load DOX through the DOX/Cu2+ chelation process. Distinctively, the synthesized PEG-HCuSNPs-DOX release the DOX/Cu2+ complexes into surrounding environment, which generate significant reactive oxygen species (ROS) in a controlled manner by near-infrared laser. The CuS nanoparticle-mediated photothermal ablation facilitates the ROS-induced cancer cell killing effect. Our current work reveals a DOX/Cu2+-mediated ROS-enhanced cell-killing effect in addition to conventional photothermal chemotherapy through the direct CuS nanoparticle-DOX complexation.

Investigating the early stages of Photosystem II assembly in Synechocystis sp. PCC 6803: isolation of CP47 and CP43 complexe

Czech Academy of Sciences Publication Activity Database

Boehm, M.; Romero, E.; Reisinger, V.; Yu, J.; Komenda, Josef; Eichacker, L. A.; Dekker, J. P.; Nixon, P. J.

2011-01-01

Roč. 286, č. 17 (2011), 14812-14819 ISSN 0021-9258 R&D Projects: GA AV ČR IAA400200801 Institutional research plan: CEZ:AV0Z50200510 Keywords : ENERGY CHLOROPHYLL STATES * ANTENNA PROTEIN COMPLEX * OXYGEN-EVOLVING CENTER Subject RIV: EE - Microbiology, Virology Impact factor: 4.773, year: 2011

Nanostructured catalysts for oxygen electroreduction based on bimetallic monoethanolamine complexes of Co(III) and Ni(II)

Czech Academy of Sciences Publication Activity Database

Pirskyy, Y.; Murafa, Nataliya; Korduban, A.M.; Šubrt, Jan

2014-01-01

Roč. 44, č. 11 (2014), s. 1193-1203 ISSN 0021-891X Institutional support: RVO:61388980 Keywords : Electrochemistry * Oxygen electroreduction * Electrocatalysts * Monoethanolamine complexes * Nanostructure Subject RIV: CA - Inorganic Chemistry Impact factor: 2.409, year: 2014

Reactive oxygen species generation in aqueous solutions containing GdVO4:Eu3+ nanoparticles and their complexes with methylene blue

Science.gov (United States)

Hubenko, Kateryna; Yefimova, Svetlana; Tkacheva, Tatyana; Maksimchuk, Pavel; Borovoy, Igor; Klochkov, Vladimir; Kavok, Nataliya; Opolonin, Oleksander; Malyukin, Yuri

2018-04-01

It this letter, we report the study of free radicals and reactive oxygen species (ROS) generation in water solutions containing gadolinium orthovanadate GdVO4:Eu3+ nanoparticles (VNPs) and their complexes with methylene blue (MB) photosensitizer. The catalytic activity was studied under UV-Vis and X-ray irradiation by three methods (conjugated dienes test, OH· radical, and singlet oxygen detection). It has been shown that the VNPs-MB complexes reveal high efficiency of ROS generation under UV-Vis irradiation associated with both high efficiency of OH· radicals generation by VNPs and singlet oxygen generation by MB due to nonradiative excitation energy transfer from VNPs to MB molecules. Contrary to that under X-ray irradiation, the strong OH . radicals scavenging by VNPs has been observed.

Oxygen - A Four Billion Year History

DEFF Research Database (Denmark)

Canfield, Donald Eugene

The air we breathe is twenty-one percent oxygen, an amount higher than on any other known world. While we may take our air for granted, Earth was not always an oxygenated planet. How did it become this way? Oxygen is the most current account of the history of atmospheric oxygen on Earth. Donald...... Canfield--one of the world's leading authorities on geochemistry, earth history, and the early oceans--covers this vast history, emphasizing its relationship to the evolution of life and the evolving chemistry of the Earth. With an accessible and colorful first-person narrative, he draws from a variety...... of fields, including geology, paleontology, geochemistry, biochemistry, animal physiology, and microbiology, to explain why our oxygenated Earth became the ideal place for life. Describing which processes, both biological and geological, act to control oxygen levels in the atmosphere, Canfield traces...

Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

Science.gov (United States)

Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

2015-07-21

The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

127I Moessbauer study of some oxygen bonded iodine(I) and iodine(III) complexes

International Nuclear Information System (INIS)

Bardhan, M.; Birchall, T.; Frampton, C.; Kapoor, P.

1988-01-01

127 I Moessbauer spectra have been recorded at 4.2 0 K for a series of oxygen bonded iodine(I) and iodine(III) complexes. The sign of the quadrupole coupling constant is dependant only on the primary arrangement of ligands about the central iodine nucleus whereas the magnitude and the asymmetry parameter are more sensitive to ligand electronegativity and type. (orig.)

Planetary Atmospheres and Evolution of Complex Life

Science.gov (United States)

Catling, D.

2014-04-01

O2 diffusion to evolve to mm size. pO2 in the range 10^3-10^4 Pa is needed to exceed the threshold of cm size for complex life with circulatory physiology. The timescale to reach pO2 10^4 Pa, or "oxygenation time", was long on the Earth ( 3.9 billion years), within almost a factor of two of the Sun's main sequence lifetime. The oxygenation time could preclude complex life on rocky planets with prodigious reducing volatiles orbiting stars that end their main sequence lives before planetary oxygenation takes place. Conversely, Earth-like planets orbiting long-lived stars are potentially favorable places for complex life.

Combinatorial Development of Water Splitting Catalysts Based on the Oxygen Evolving Complex of Photosystem II

Energy Technology Data Exchange (ETDEWEB)

Woodbury, Neal [Arizona State University

2010-03-31

The use of methods to create large arrays of potential catalysts for the reaction H2O ½ O2 + 2H+ on the anode of an electrolysis system were investigated. This reaction is half of the overall reaction involved in the splitting of water into hydrogen and oxygen gas. This method consisted of starting with an array of electrodes and developing patterned electrochemical approaches for creating a different, defined peptide at each position in the array. Methods were also developed for measuring the rate of reaction at each point in the array. In this way, the goal was to create and then tests many thousands of possible catalysts simultaneously. This type of approach should lead to an ability to optimize catalytic activity systematically, by iteratively designing and testing new libraries of catalysts. Optimization is important to decrease energy losses (over-potentials) associated with the water splitting reaction and thus for the generation of hydrogen. Most of the efforts in this grant period were focused on developing the chemistry and analytical methods required to create pattern peptide formation either using a photolithography approach or an electrochemical approach for dictating the positions of peptide bond formation. This involved testing a large number of different reactions and conditions. We have been able to find conditions that have allowed us to pattern peptide bond formation on both glass slides using photolithographic methods and on electrode arrays made by the company Combimatrix. Part of this effort involved generating novel approaches for performing mass spectroscopy directly from the patterned arrays. We have also been able to demonstrate the ability to measure current at each electrode due to electrolysis of water. This was performed with customized instrumentation created in collaboration with Combimatrix. In addition, several different molecular designs for peptides that bound metals (primarily Mn) were developed and synthesized and metal

On the Critical Role of Divergent Selection in Evolvability

Directory of Open Access Journals (Sweden)

Joel Lehman

2016-08-01

Full Text Available An ambitious goal in evolutionary robotics is to evolve increasingly complex robotic behaviors with minimal human design effort. Reaching this goal requires evolutionary algorithms that can unlock from genetic encodings their latent potential for evolvability. One issue clouding this goal is conceptual confusion about evolvability, which often obscures the aspects of evolvability that are important or desirable. The danger from such confusion is that it may establish unrealistic goals for evolvability that prove unproductive in practice. An important issue separate from conceptual confusion is the common misalignment between selection and evolvability in evolutionary robotics. While more expressive encodings can represent higher-level adaptations (e.g. sexual reproduction or developmental systems that increase long-term evolutionary potential (i.e. evolvability, realizing such potential requires gradients of fitness and evolvability to align. In other words, selection is often a critical factor limiting increasing evolvability. Thus, drawing from a series of recent papers, this article seeks to both (1 clarify and focus the ways in which the term evolvability is used within artificial evolution, and (2 argue for the importance of one type of selection, i.e. divergent selection, for enabling evolvability. The main argument is that there is a fundamental connection between divergent selection and evolvability (on both the individual and population level that does not hold for typical goal-oriented selection. The conclusion is that selection pressure plays a critical role in realizing the potential for evolvability, and that divergent selection in particular provides a principled mechanism for encouraging evolvability in artificial evolution.

EVOLVE 2014 International Conference

CERN Document Server

Tantar, Emilia; Sun, Jian-Qiao; Zhang, Wei; Ding, Qian; Schütze, Oliver; Emmerich, Michael; Legrand, Pierrick; Moral, Pierre; Coello, Carlos

2014-01-01

This volume encloses research articles that were presented at the EVOLVE 2014 International Conference in Beijing, China, July 1–4, 2014.The book gathers contributions that emerged from the conference tracks, ranging from probability to set oriented numerics and evolutionary computation; all complemented by the bridging purpose of the conference, e.g. Complex Networks and Landscape Analysis, or by the more application oriented perspective. The novelty of the volume, when considering the EVOLVE series, comes from targeting also the practitioner’s view. This is supported by the Machine Learning Applied to Networks and Practical Aspects of Evolutionary Algorithms tracks, providing surveys on new application areas, as in the networking area and useful insights in the development of evolutionary techniques, from a practitioner’s perspective. Complementary to these directions, the conference tracks supporting the volume, follow on the individual advancements of the subareas constituting the scope of the confe...

Determination of non-metallic elements in actinide complexes by oxygen flask combustion (OFC): chlorine and fluorine

International Nuclear Information System (INIS)

Ruikar, P.B.; Nagar, M.S.; Subramanian, M.S.

1989-01-01

The oxygen flask combustion followed by ion selective electrode measurement has been found to be the most suitable from the point of view of elegance and simplicity for the determination of chlorine and fluorine in actinide complexes. The method has been found to be particularly suitable for glove box adaptation. This report describes the determination of chlorine and fluorine in several uranium complexes, some plutonium complexes and organic analytical standards by this method. The precision and accuracy of the measurements in the milligram level has been found to be quite satisfactory. (author). 16 refs., 11 tabs

Interstellar Chemistry Special Feature: The chemistry in circumstellar envelopes of evolved stars: Following the origin of the elements to the origin of life

Science.gov (United States)

Ziurys, Lucy M.

2006-08-01

Mass loss from evolved stars results in the formation of unusual chemical laboratories: circumstellar envelopes. Such envelopes are found around carbon- and oxygen-rich asymptotic giant branch stars and red supergiants. As the gaseous material of the envelope flows from the star, the resulting temperature and density gradients create a complex chemical environment involving hot, thermodynamically controlled synthesis, molecule "freeze-out," shock-initiated reactions, and photochemistry governed by radical mechanisms. In the circumstellar envelope of the carbon-rich star IRC+10216, >50 different chemical compounds have been identified, including such exotic species as C8H, C3S, SiC3, and AlNC. The chemistry here is dominated by molecules containing long carbon chains, silicon, and metals such as magnesium, sodium, and aluminum, which makes it quite distinct from that found in molecular clouds. The molecular composition of the oxygen-rich counterparts is not nearly as well explored, although recent studies of VY Canis Majoris have resulted in the identification of HCO+, SO2, and even NaCl in this object, suggesting chemical complexity here as well. As these envelopes evolve into planetary nebulae with a hot, exposed central star, synthesis of molecular ions becomes important, as indicated by studies of NGC 7027. Numerous species such as HCO+, HCN, and CCH are found in old planetary nebulae such as the Helix. This "survivor" molecular material may be linked to the variety of compounds found recently in diffuse clouds. Organic molecules in dense interstellar clouds may ultimately be traced back to carbon-rich fragments originally formed in circumstellar shells.

An oxygen-rich dust disk surrounding an evolved star in the Red Rectangle

NARCIS (Netherlands)

Waters, LBFM; Waelkens, C; van Winckel, H; Molster, FJ; Tielens, AGGM; van Loon, JT; Morris, PW; Cami, J; Bouwman, J; de Koter, A; de Jong, T; de Graauw, T

1998-01-01

The Red Rectangle(1) is the prototype of a class of carbon-rich reflection nebulae surrounding low-mass stars in the final stages of evolution. The central star of this nebula has ejected most of its layers (during the red-giant phase), which now form the surrounding cloud, and is rapidly evolving

Organodioxygen complexes of some heavy metal ions and their oxygen transfer reactions

International Nuclear Information System (INIS)

Tarafder, M.T.H.; Mei Ling; Gino Mariotto

2003-09-01

Several novel organodioxygen complexes of lanthanide ions, viz., lanthanum(m) and cerium(IV) have been synthesized containing a number of organic co- ligands. The complexes characterized were, [La(0 2 )(det)(N0 3 ) 2 ] (1), [La(O 2 )(tet)(NO 3 ) 2 ] (2), [La(O 2 )(C 5 H 5 N)2NO 3 ] (3), [La(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 2 ] (4), [La(0 2 )(OPPh 3 ) 2 (N0 3 ) 2 ] (5), [La(O 2 ) 2 (NH 2 CH 2 CH 2 NH 2 ) 2 NO 3 ] (6), [La(O 2 )(PPh 3 ) 2 (NO 3 ) 2 ] (7) and [Ce(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 3 ] (8). IR and Raman spectra revealed that (3) was a peroxo complex while the others were, in particular, superoxo type. The IR spectrum of (3) gives V 1 (O-O) at 851 cm -1 while the Raman spectra of (4), (5), (7) and (8) give V 1 (O 2 ) bands at 1046 cm -1 , 1032 cm 1 , 1100 cm -1 and 1046 cm -1 , respectively. The oxygen transfer reactions of two selected complexes were carried out under stoichiometric conditions. The complex containing a bidentate ligand, (6), was found to oxidize triphenylphosphine and trans-stilbene to their oxides while the complex containing tridentate ligand (1) was stable and inert towards oxidation. (author)

Reactive Oxygen Species on the Early Earth and Survival of Bacteria

Science.gov (United States)

Balk, Melikea; Mason, Paul; Stams, Alfons J. M.; Smidt, Hauke; Freund, Friedemann; Rothschild, Lynn

2011-01-01

An oxygen-rich atmosphere appears to have been a prerequisite for complex, multicellular life to evolve on Earth and possibly elsewhere in the Universe. However it remains unclear how free oxygen first became available on the early Earth. A potentially important, and as yet poorly constrained pathway, is the production of oxygen through the weathering of rocks and release into the near-surface environment. Reactive Oxygen Species (ROS), as precursors to molecular oxygen, are a key step in this process, and may have had a decisive impact on the evolution of life, present and past. ROS are generated from minerals in igneous rocks during hydrolysis of peroxy defects, which consist of pairs of oxygen anions oxidized to the valence state -1 and during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that, despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, organisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defences against the potentially dangerous, even lethal effects of oxygen and its derived ROS. Conversely it appears that microorganisms learned to take advantage of the enormous reactive potential and energy gain provided by nascent oxygen. We investigate how oxygen might be released through weathering. We test microorganisms in contact with rock surfaces and iron sulphides. We model bacteria such as Deionococcus radiodurans and Desulfotomaculum, Moorella and Bacillus species for their ability to grow or survive in the presence of ROS. We examine how early Life might have adapted to oxygen.

Cocaine- and amphetamine-regulated transcript peptide increases mitochondrial respiratory chain complex II activity and protects against oxygen-glucose deprivation in neurons.

Science.gov (United States)

Sha, Dujuan; Wang, Luna; Zhang, Jun; Qian, Lai; Li, Qiming; Li, Jin; Qian, Jian; Gu, Shuangshuang; Han, Ling; Xu, Peng; Xu, Yun

2014-09-25

The mechanisms of ischemic stroke, a main cause of disability and death, are complicated. Ischemic stroke results from the interaction of various factors including oxidative stress, a key pathological mechanism that plays an important role during the acute stage of ischemic brain injury. This study demonstrated that cocaine- and amphetamine-regulated transcript (CART) peptide, specifically CART55-102, increased the survival rate, but decreased the mortality of neurons exposed to oxygen-glucose deprivation (OGD), in a dose-dependent manner. The above-mentioned effects of CART55-102 were most significant at 0.4nM. These results indicated that CART55-102 suppressed neurotoxicity and enhanced neuronal survival after oxygen-glucose deprivation. CART55-102 (0.4nM) significantly diminished reactive oxygen species levels and markedly increased the activity of mitochondrial respiratory chain complex II in oxygen-glucose deprived neurons. In summary, CART55-102 suppressed oxidative stress in oxygen-glucose deprived neurons, possibly through elevating the activity of mitochondrial respiratory chain complex II. This result provides evidence for the development of CART55-102 as an antioxidant drug. Copyright © 2014 Elsevier B.V. All rights reserved.

Uniting sex and eukaryote origins in an emerging oxygenic world.

Science.gov (United States)

Gross, Jeferson; Bhattacharya, Debashish

2010-08-23

, prokaryotic DNA recombination, and the universality of nuclear-mediated meiotic activities might corroborate the hypothesis that sex and the nucleus evolved to support DNA repair. Oxygen tolerance emerges as an important principle to investigate eukaryogenesis. The evolution of eukaryotic complexity might be best understood as a synergic process between key evolutionary innovations, of which meiosis (sex) played a central role. This manuscript was reviewed by Eugene V. Koonin, Anthony M. Poole, and Gáspár Jékely.

Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

KAUST Repository

Anneser, Markus R.

2016-02-26

The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.

Trading Control Intelligence for Physical Intelligence: Muscle Drives in Evolved Virtual Creatures

DEFF Research Database (Denmark)

Lessin, Dan; Fussell, Don; Miikkulainen, Risto

2014-01-01

Traditional evolved virtual creatures [12] are actuated using unevolved, uniform, invisible drives at joints between rigid segments. In contrast, this paper shows how such conven- tional actuators can be replaced by evolvable muscle drives that are a part of the creature’s physical structure....... This design is important for two reasons: First, the con- trol intelligence is made visible in the purposeful develop- ment of muscle density, orientation, attachment points, and size. Second, the complexity that needs to be evolved for the brain to control the actuators is reduced, and in some cases can...... be essentially eliminated, thus freeing brain power for higher-level functions. Such designs may thus make it pos- sible to create more complex behavior than would otherwise be achievable....

Exploring the evolutionary mechanism of complex supply chain systems using evolving hypergraphs

Science.gov (United States)

Suo, Qi; Guo, Jin-Li; Sun, Shiwei; Liu, Han

2018-01-01

A new evolutionary model is proposed to describe the characteristics and evolution pattern of supply chain systems using evolving hypergraphs, in which nodes represent enterprise entities while hyperedges represent the relationships among diverse trades. The nodes arrive at the system in accordance with a Poisson process, with the evolving process incorporating the addition of new nodes, linking of old nodes, and rewiring of links. Grounded in the Poisson process theory and continuum theory, the stationary average hyperdegree distribution is shown to follow a shifted power law (SPL), and the theoretical predictions are consistent with the results of numerical simulations. Testing the impact of parameters on the model yields a positive correlation between hyperdegree and degree. The model also uncovers macro characteristics of the relationships among enterprises due to the microscopic interactions among individuals.

Trace Oxygen Sensitive Material Based on Two Porphyrin Derivatives in a Heterodimeric Complex

Directory of Open Access Journals (Sweden)

Eugenia Fagadar-Cosma

2017-10-01

Full Text Available The successful preparation of a novel dimer complex formed between 5,10,15,20-tetrakis(3,4-dimethoxyphenyl-porphyrin Fe(III chloride and (5,10,15,20-tetraphenylporphinato dichlorophosphorus(V chloride using the well-known reactivity of the P–X bond is reported. The obtained complex was characterized by UV-vis, Fourier transform infrared spectroscopy (FT-IR, fluorescence, 1H-NMR, 13C-NMR, and 31P-NMR spectroscopic techniques and also by additional Heteronuclear Single Quantum Coherence (HSQC and Heteronuclear Multiple Bond Correlation (HMBC experiments in order to correctly assign the NMR signals. Scanning electron microscopy (SEM and EDX quantifications completed the characterizations. This novel porphyrin dimer complex demonstrated fluorescence sensing of H2O2 in water for low oxygen concentrations in the range of 40–90 µM proving medical relevance for early diagnosis of diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and even cancer because higher concentrations of H2O2 than 50 μM are consideredcytotoxic for life. Due to its optical properties, this novel metalloporphyrin–porphyrin based complex is expected to show PDT and bactericidal activity under visible-light irradiation.

Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

Science.gov (United States)

Simon, J. I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

2014-01-01

Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

Root Effect Haemoglobins in Fish May Greatly Enhance General Oxygen Delivery Relative to Other Vertebrates.

Directory of Open Access Journals (Sweden)

Jodie L Rummer

Full Text Available The teleost fishes represent over half of all extant vertebrates; they occupy nearly every body of water and in doing so, occupy a diverse array of environmental conditions. We propose that their success is related to a unique oxygen (O2 transport system involving their extremely pH-sensitive haemoglobin (Hb. A reduction in pH reduces both Hb-O2 affinity (Bohr effect and carrying capacity (Root effect. This, combined with a large arterial-venous pH change (ΔpHa-v relative to other vertebrates, may greatly enhance tissue oxygen delivery in teleosts (e.g., rainbow trout during stress, beyond that in mammals (e.g., human. We generated oxygen equilibrium curves (OECs at five different CO2 tensions for rainbow trout and determined that, when Hb-O2 saturation is 50% or greater, the change in oxygen partial pressure (ΔPO2 associated with ΔpHa-v can exceed that of the mammalian Bohr effect by at least 3-fold, but as much as 21-fold. Using known ΔpHa-v and assuming a constant arterial-venous PO2 difference (Pa-vO2, Root effect Hbs can enhance O2 release to the tissues by 73.5% in trout; whereas, the Bohr effect alone is responsible for enhancing O2 release by only 1.3% in humans. Disequilibrium states are likely operational in teleosts in vivo, and therefore the ΔpHa-v, and thus enhancement of O2 delivery, could be even larger. Modeling with known Pa-vO2 in fish during exercise and hypoxia indicates that O2 release from the Hb and therefore potentially tissue O2 delivery may double during exercise and triple during some levels of hypoxia. These characteristics may be central to performance of athletic fish species such as salmonids, but may indicate that general tissue oxygen delivery may have been the incipient function of Root effect Hbs in fish, a trait strongly associated with the adaptive radiation of teleosts.

EvoCommander: A Novel Game Based on Evolving and Switching Between Artificial Brains

DEFF Research Database (Denmark)

Jallov, D.; Risi, S.; Togelius, J.

2016-01-01

Neuroevolution (i.e. evolving artificial neural networks (ANNs) through evolutionary algorithms) has shown promise in evolving agents and robot controllers, which display complex behaviours and can adapt to their environments. These properties are also relevant to video games, since they can...

Evaluation and testing methodology for evolving entertainment systems

NARCIS (Netherlands)

Jurgelionis, A.; Bellotti, F.; IJsselsteijn, W.A.; Kort, de Y.A.W.; Bernhaupt, R.; Tscheligi, M.

2007-01-01

This paper presents a testing and evaluation methodology for evolving pervasive gaming and multimedia systems. We introduce the Games@Large system, a complex gaming and multimedia architecture comprised of a multitude of elements: heterogeneous end user devices, wireless and wired network

Devonian rise in atmospheric oxygen correlated to the radiations of terrestrial plants and large predatory fish

DEFF Research Database (Denmark)

Dahl, Tais Wittchen; Hammarlund, Emma; Anbar, Ariel D.

2010-01-01

after the initial rise of animals and, therefore, suggesting that early metazoans evolved in a relatively low oxygen environment. This later oxygenation correlates with the diversification of vascular plants, which likely contributed to increased oxygenation through the enhanced burial of organic carbon...

Formation of mixed ligand complexes of UO22+ involving some nitrogen and oxygen donor ligands

International Nuclear Information System (INIS)

Singh, Mamta; Ram Nayan

1996-01-01

The complexation reactions of UO 2 2+ ion with nitrogen and oxygen donor ligands, 1-amino-2-naphthol-4-sulphonic acid, o-aminophenol (ap), 2-hydroxybenzoic acid (sa), 3-carboxy-4-hydroxybenzenesulphonic acid (ss) and 1,2-dihydroxybenzene (ca) have been investigated in aqueous solution employing the pH-titration technique. Analysis of the experimental data recorded at 25 degC and at an ionic strength of 0.10 M KNO 3 indicates formation of binary, hydroxo and ternary complexes of uranium. Formation constant values of the existing species have been evaluated and the results have been discussed. (author). 21 refs., 2 figs., 2 tabs

Evolvable Neural Software System

Science.gov (United States)

Curtis, Steven A.

2009-01-01

The Evolvable Neural Software System (ENSS) is composed of sets of Neural Basis Functions (NBFs), which can be totally autonomously created and removed according to the changing needs and requirements of the software system. The resulting structure is both hierarchical and self-similar in that a given set of NBFs may have a ruler NBF, which in turn communicates with other sets of NBFs. These sets of NBFs may function as nodes to a ruler node, which are also NBF constructs. In this manner, the synthetic neural system can exhibit the complexity, three-dimensional connectivity, and adaptability of biological neural systems. An added advantage of ENSS over a natural neural system is its ability to modify its core genetic code in response to environmental changes as reflected in needs and requirements. The neural system is fully adaptive and evolvable and is trainable before release. It continues to rewire itself while on the job. The NBF is a unique, bilevel intelligence neural system composed of a higher-level heuristic neural system (HNS) and a lower-level, autonomic neural system (ANS). Taken together, the HNS and the ANS give each NBF the complete capabilities of a biological neural system to match sensory inputs to actions. Another feature of the NBF is the Evolvable Neural Interface (ENI), which links the HNS and ANS. The ENI solves the interface problem between these two systems by actively adapting and evolving from a primitive initial state (a Neural Thread) to a complicated, operational ENI and successfully adapting to a training sequence of sensory input. This simulates the adaptation of a biological neural system in a developmental phase. Within the greater multi-NBF and multi-node ENSS, self-similar ENI s provide the basis for inter-NBF and inter-node connectivity.

Zinc(II) complexes with intramolecular amide oxygen coordination as models of metalloamidases.

Science.gov (United States)

Rivas, Juan C Mareque; Salvagni, Emiliano; Prabaharan, Ravi; de Rosales, Rafael Torres Martin; Parsons, Simon

2004-01-07

Polydentate ligands (6-R1-2-pyridylmethyl)-R2(R1= NHCOtBu, R2= bis(2-pyridylmethyl)amine L1, bis(2-(methylthio)ethyl)amine L2 and N(CH2CH2)2S L3) form mononuclear zinc(II) complexes with intramolecular amide oxygen coordination and a range of coordination environments. Thus, the reaction of Zn(ClO4)2.6H2O with L1-3 in acetonitrile affords [(L)Zn](ClO4)2(L=L1, 1; L2, 2) and [(L3)Zn(H2O)(NCCH3)](ClO4)2 3. The simultaneous amide/water binding in resembles the motif that has been proposed to be involved in the double substrate/nucleophile Lewis acidic activation and positioning mechanism of amide bond hydrolysis in metallopeptidases. X-ray diffraction, 1H and 13C NMR and IR data suggests that the strength of amide oxygen coordination follows the trend 1>2 >3. L1-3 and undergo cleavage of the tert-butylamide upon addition of Me4NOH.5H2O (1 equiv.) in methanol at 50(1)degrees C. The rate of amide cleavage follows the order 1> 2> 3, L1-3. The extent by which the amide cleavage reaction is accelerated in 1-3 relative to the free ligands, L1-3, is correlated with the strength of amide oxygen binding and Lewis acidity of the zinc(II) centre in deduced from the X-ray, NMR and IR studies.

Mitochondrial Complex IV Subunit 4 Isoform 2 Is Essential for Acute Pulmonary Oxygen Sensing.

Science.gov (United States)

Sommer, Natascha; Hüttemann, Maik; Pak, Oleg; Scheibe, Susan; Knoepp, Fenja; Sinkler, Christopher; Malczyk, Monika; Gierhardt, Mareike; Esfandiary, Azadeh; Kraut, Simone; Jonas, Felix; Veith, Christine; Aras, Siddhesh; Sydykov, Akylbek; Alebrahimdehkordi, Nasim; Giehl, Klaudia; Hecker, Matthias; Brandes, Ralf P; Seeger, Werner; Grimminger, Friedrich; Ghofrani, Hossein A; Schermuly, Ralph T; Grossman, Lawrence I; Weissmann, Norbert

2017-08-04

Acute pulmonary oxygen sensing is essential to avoid life-threatening hypoxemia via hypoxic pulmonary vasoconstriction (HPV) which matches perfusion to ventilation. Hypoxia-induced mitochondrial superoxide release has been suggested as a critical step in the signaling pathway underlying HPV. However, the identity of the primary oxygen sensor and the mechanism of superoxide release in acute hypoxia, as well as its relevance for chronic pulmonary oxygen sensing, remain unresolved. To investigate the role of the pulmonary-specific isoform 2 of subunit 4 of the mitochondrial complex IV (Cox4i2) and the subsequent mediators superoxide and hydrogen peroxide for pulmonary oxygen sensing and signaling. Isolated ventilated and perfused lungs from Cox4i2 -/- mice lacked acute HPV. In parallel, pulmonary arterial smooth muscle cells (PASMCs) from Cox4i2 -/- mice showed no hypoxia-induced increase of intracellular calcium. Hypoxia-induced superoxide release which was detected by electron spin resonance spectroscopy in wild-type PASMCs was absent in Cox4i2 -/- PASMCs and was dependent on cysteine residues of Cox4i2. HPV could be inhibited by mitochondrial superoxide inhibitors proving the functional relevance of superoxide release for HPV. Mitochondrial hyperpolarization, which can promote mitochondrial superoxide release, was detected during acute hypoxia in wild-type but not Cox4i2 -/- PASMCs. Downstream signaling determined by patch-clamp measurements showed decreased hypoxia-induced cellular membrane depolarization in Cox4i2 -/- PASMCs compared with wild-type PASMCs, which could be normalized by the application of hydrogen peroxide. In contrast, chronic hypoxia-induced pulmonary hypertension and pulmonary vascular remodeling were not or only slightly affected by Cox4i2 deficiency, respectively. Cox4i2 is essential for acute but not chronic pulmonary oxygen sensing by triggering mitochondrial hyperpolarization and release of mitochondrial superoxide which, after conversion

Oxygen Sensing by the Hybrid Langmuir-Blodgett Films of Iridium(III Complexes and Synthetic Saponite on the Basis of Energy Transfer

Directory of Open Access Journals (Sweden)

Hisako Sato

2017-09-01

Full Text Available An ultra-thin hybrid film of amphiphilic iridium(III complexes and synthetic saponite was manipulated by means of the modified Langmuir-Blodgett method. In the film deposited onto a quartz substrate, the external mixed molecular layer of amphiphilic iridium(III complexes was reinforced by the inner layer of exfoliated synthetic saponite. As components of the molecular layer, two iridium(III complexes were used: [Ir(dfppy2(dc9bpy]+ (dfppyH = 2-(4′,6′-difluorophenyl pyridine; dc9bpy = 4,4′-dinonyl-2,2′-bipyridine (denoted as DFPPY and [Ir(piq2(dc9bpy]+ (piqH = 1-phenyisoquinoline denoted as PIQ. The emission spectra from the films changed from blue to red maxima with the decrease of a ratio of DFPPY/PIQ due to the energy transfer from excited DFPPY to PIQ. The intensity of red decreased with the increase of oxygen pressure through the quenching of excited iridium(III complexes, promising a possibility as an oxygen-sensing film.

Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

Science.gov (United States)

McCrory, Charles C L; Jung, Suho; Peters, Jonas C; Jaramillo, Thomas F

2013-11-13

Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.

Design of a lunar oxygen production plant

Science.gov (United States)

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.

Nature of oxygen donors and radiation defects in oxygen-doped germanium

International Nuclear Information System (INIS)

Fukuoka, Noboru; Atobe, Kozo; Honda, Makoto; Matsuda, Koji.

1991-01-01

The nature of oxygen donors and radiation defects in oxygen-doped germanium were studied through measurements of the infrared absorption spectrum, deep level transient spectroscopy spectrum and carrier concentration. It is revealed that a new donor is not formed in oxygen-doped germanium. An A-center (interstitial oxygen-vacancy pair) forms a complex with a thermal donor in its annealing stage at 60degC-140degC. The introduction rate of defects by 1.5 MeV electron irradiation was enhanced in thermal-donor-doped samples. (author)

Measuring oxygen uptake in fishes with bimodal respiration.

Science.gov (United States)

Lefevre, S; Bayley, M; McKenzie, D J

2016-01-01

Respirometry is a robust method for measurement of oxygen uptake as a proxy for metabolic rate in fishes, and how species with bimodal respiration might meet their demands from water v. air has interested researchers for over a century. The challenges of measuring oxygen uptake from both water and air, preferably simultaneously, have been addressed in a variety of ways, which are briefly reviewed. These methods are not well-suited for the long-term measurements necessary to be certain of obtaining undisturbed patterns of respiratory partitioning, for example, to estimate traits such as standard metabolic rate. Such measurements require automated intermittent-closed respirometry that, for bimodal fishes, has only recently been developed. This paper describes two approaches in enough detail to be replicated by the interested researcher. These methods are for static respirometry. Measuring oxygen uptake by bimodal fishes during exercise poses specific challenges, which are described to aid the reader in designing experiments. The respiratory physiology and behaviour of air-breathing fishes is very complex and can easily be influenced by experimental conditions, and some general considerations are listed to facilitate the design of experiments. Air breathing is believed to have evolved in response to aquatic hypoxia and, probably, associated hypercapnia. The review ends by considering what realistic hypercapnia is, how hypercapnic tropical waters can become and how this might influence bimodal animals' gas exchange. © 2015 The Fisheries Society of the British Isles.

The secretions of oviduct epithelial cells increase the equine in vitro fertilization rate: are osteopontin, atrial natriuretic peptide A and oviductin involved?

Directory of Open Access Journals (Sweden)

Canepa Sylvie

2009-11-01

Full Text Available Abstract Background Oviduct epithelial cells (OEC co-culture promotes in vitro fertilization (IVF in human, bovine and porcine species, but no data are available from equine species. Yet, despite numerous attempts, equine IVF rates remain low. Our first aim was to verify a beneficial effect of the OEC on equine IVF. In mammals, oviductal proteins have been shown to interact with gametes and play a role in fertilization. Thus, our second aim was to identify the proteins involved in fertilization in the horse. Methods & results In the first experiment, we co-incubated fresh equine spermatozoa treated with calcium ionophore and in vitro matured equine oocytes with or without porcine OEC. We showed that the presence of OEC increases the IVF rates. In the subsequent experiments, we co-incubated equine gametes with OEC and we showed that the IVF rates were not significantly different between 1 gametes co-incubated with equine vs porcine OEC, 2 intact cumulus-oocyte complexes vs denuded oocytes, 3 OEC previously stimulated with human Chorionic Gonadotropin, Luteinizing Hormone and/or oestradiol vs non stimulated OEC, 4 in vivo vs in vitro matured oocytes. In order to identify the proteins responsible for the positive effect of OEC, we first searched for the presence of the genes encoding oviductin, osteopontin and atrial natriuretic peptide A (ANP A in the equine genome. We showed that the genes coding for osteopontin and ANP A are present. But the one for oviductin either has become a pseudogene during evolution of horse genome or has been not well annotated in horse genome sequence. We then showed that osteopontin and ANP A proteins are present in the equine oviduct using a surface plasmon resonance biosensor, and we analyzed their expression during oestrus cycle by Western blot. Finally, we co-incubated equine gametes with or without purified osteopontin or synthesized ANP A. No significant effect of osteopontin or ANP A was observed, though

Advertising, product quality, and complex evolving marketing systems

OpenAIRE

Verbeke, Willem

1992-01-01

textabstractThe paper analyses the advertising as power vs. advertising as information controversy as well as its recent empirical testing. It is stressed that this distinction focuses too much on the interaction between consumer and manufacturer while ignoring the retailer as an important stake-holder. To compensate for this lack, a complex marketing system perspective is introduced in which consumer, retailer, and manufacturer interact. However, these complex marketing systems might drift t...

Development of a Novel Cu(II Complex Modified Electrode and a Portable Electrochemical Analyzer for the Determination of Dissolved Oxygen (DO in Water

Directory of Open Access Journals (Sweden)

Salvatore Gianluca Leonardi

2016-04-01

Full Text Available The development of an electrochemical dissolved oxygen (DO sensor based on a novel Cu(II complex-modified screen printed carbon electrode is reported. The voltammetric behavior of the modified electrode was investigated at different scan rates and oxygen concentrations in PBS (pH = 7. An increase of cathodic current (at about −0.4 vs. Ag/AgCl with the addition of oxygen was observed. The modified Cu(II complex electrode was demonstrated for the determination of DO in water using chronoamperometry. A small size and low power consumption home-made portable electrochemical analyzer based on custom electronics for sensor interfacing and operating in voltammetry and amperometry modes has been also designed and fabricated. Its performances in the monitoring of DO in water were compared with a commercial one.

High-resolution method for evolving complex interface networks

Science.gov (United States)

Pan, Shucheng; Hu, Xiangyu Y.; Adams, Nikolaus A.

2018-04-01

In this paper we describe a high-resolution transport formulation of the regional level-set approach for an improved prediction of the evolution of complex interface networks. The novelty of this method is twofold: (i) construction of local level sets and reconstruction of a global level set, (ii) local transport of the interface network by employing high-order spatial discretization schemes for improved representation of complex topologies. Various numerical test cases of multi-region flow problems, including triple-point advection, single vortex flow, mean curvature flow, normal driven flow, dry foam dynamics and shock-bubble interaction show that the method is accurate and suitable for a wide range of complex interface-network evolutions. Its overall computational cost is comparable to the Semi-Lagrangian regional level-set method while the prediction accuracy is significantly improved. The approach thus offers a viable alternative to previous interface-network level-set method.

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands.

Science.gov (United States)

Ng, Ho-Yuen; Cheung, Wai-Man; Kwan Huang, Enrique; Wong, Kang-Long; Sung, Herman H-Y; Williams, Ian D; Leung, Wa-Hung

2015-11-14

Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bu(n)4N][Ru(N)Cl4] and KN(Bu(t)2PS)2, presumably via sulfur atom transfer from [N(Bu(t)2PS)2](-) to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt(-) = [Co(η(5)-C5H5){P(O)(LOEt)2}3](-)) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bu(n)4N][Ru(N)Cl4] with KN(R2PS)2 produced Ru(IV)-Ru(IV)μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pr(i) (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance Ru(III)-Ru(IV)μ-nitrido complex [Ru2(μ-N){N(Bu(t)2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the Ru(IV)-Ru(IV) complex [Ru2(μ-N){N(Bu(t)2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

Evolution of networks for body plan patterning; interplay of modularity, robustness and evolvability.

Directory of Open Access Journals (Sweden)

Kirsten H Ten Tusscher

2011-10-01

Full Text Available A major goal of evolutionary developmental biology (evo-devo is to understand how multicellular body plans of increasing complexity have evolved, and how the corresponding developmental programs are genetically encoded. It has been repeatedly argued that key to the evolution of increased body plan complexity is the modularity of the underlying developmental gene regulatory networks (GRNs. This modularity is considered essential for network robustness and evolvability. In our opinion, these ideas, appealing as they may sound, have not been sufficiently tested. Here we use computer simulations to study the evolution of GRNs' underlying body plan patterning. We select for body plan segmentation and differentiation, as these are considered to be major innovations in metazoan evolution. To allow modular networks to evolve, we independently select for segmentation and differentiation. We study both the occurrence and relation of robustness, evolvability and modularity of evolved networks. Interestingly, we observed two distinct evolutionary strategies to evolve a segmented, differentiated body plan. In the first strategy, first segments and then differentiation domains evolve (SF strategy. In the second scenario segments and domains evolve simultaneously (SS strategy. We demonstrate that under indirect selection for robustness the SF strategy becomes dominant. In addition, as a byproduct of this larger robustness, the SF strategy is also more evolvable. Finally, using a combined functional and architectural approach, we determine network modularity. We find that while SS networks generate segments and domains in an integrated manner, SF networks use largely independent modules to produce segments and domains. Surprisingly, we find that widely used, purely architectural methods for determining network modularity completely fail to establish this higher modularity of SF networks. Finally, we observe that, as a free side effect of evolving segmentation

Thorium(IV) and zirconium(IV) complexes of oxygen donor ligands. Pt. 12

International Nuclear Information System (INIS)

Agarwal, R.K.; Jain, P.C.; Kapur, V.; Sharma, S.; Srivastava, A.K.

1980-01-01

Crystalline thorium (IV) chelates with mono N-oxides of 2,2'-bipyridine (bipyNO) and 1,10-phenanthroline (phenNO), ThX 4 x 2L(X = Cl,Br,NO 3 or NCS) and ThX 4 x 3L(X = I or ClO 4 and L = bipyNO or phenNO) have been synthesised and characterized on the basis of i.r. spectra, molar conductance, molecular weights, t.g.a. and d.t.a. data. All the complexes are weakly diamagnetic and contain bipyNO and phenNO bonded to thorium(IV) through nitrogen and oxygen. The coordination number of thorium(IV) varies from six to twelve depending on the nature of the anions. (orig.) [de

An evolving user-oriented model of Internet health information seeking.

Science.gov (United States)

Gaie, Martha J

2006-01-01

This paper presents an evolving user-oriented model of Internet health information seeking (IS) based on qualitative data collected from 22 lung cancer (LC) patients and caregivers. This evolving model represents information search behavior as more highly individualized, complex, and dynamic than previous models, including pre-search psychological activity, use of multiple heuristics throughout the process, and cost-benefit evaluation of search results. This study's findings suggest that IS occurs in four distinct phases: search initiation/continuation, selective exposure, message processing, and message evaluation. The identification of these phases and the heuristics used within them suggests a higher order of complexity in the decision-making processes that underlie IS, which could lead to the development of a conceptual framework that more closely reflects the complex nature of contextualized IS. It also illustrates the advantages of using qualitative methods to extract more subtle details of the IS process and fill in the gaps in existing models.

Evolving Systems: Adaptive Key Component Control and Inheritance of Passivity and Dissipativity

Science.gov (United States)

Frost, S. A.; Balas, M. J.

2010-01-01

We propose a new framework called Evolving Systems to describe the self-assembly, or autonomous assembly, of actively controlled dynamical subsystems into an Evolved System with a higher purpose. Autonomous assembly of large, complex flexible structures in space is a target application for Evolving Systems. A critical requirement for autonomous assembling structures is that they remain stable during and after assembly. The fundamental topic of inheritance of stability, dissipativity, and passivity in Evolving Systems is the primary focus of this research. In this paper, we develop an adaptive key component controller to restore stability in Nonlinear Evolving Systems that would otherwise fail to inherit the stability traits of their components. We provide sufficient conditions for the use of this novel control method and demonstrate its use on an illustrative example.

Oxygen concentration inside a functioning photosynthetic cell.

Science.gov (United States)

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.

Evolvability Search: Directly Selecting for Evolvability in order to Study and Produce It

DEFF Research Database (Denmark)

Mengistu, Henok; Lehman, Joel Anthony; Clune, Jeff

2016-01-01

of evolvable digital phenotypes. Although some types of selection in evolutionary computation indirectly encourage evolvability, one unexplored possibility is to directly select for evolvability. To do so, we estimate an individual's future potential for diversity by calculating the behavioral diversity of its...... immediate offspring, and select organisms with increased offspring variation. While the technique is computationally expensive, we hypothesized that direct selection would better encourage evolvability than indirect methods. Experiments in two evolutionary robotics domains confirm this hypothesis: in both...... domains, such Evolvability Search produces solutions with higher evolvability than those produced with Novelty Search or traditional objective-based search algorithms. Further experiments demonstrate that the higher evolvability produced by Evolvability Search in a training environment also generalizes...

Impurities of oxygen in silicon

International Nuclear Information System (INIS)

Gomes, V.M.S.

1985-01-01

The electronic structure of oxygen complex defects in silicon, using molecular cluster model with saturation by watson sphere into the formalism of Xα multiple scattering method is studied. A systematic study of the simulation of perfect silicon crystal and an analysis of the increasing of atom number in the clusters are done to choose the suitable cluster for the calculations. The divacancy in three charge states (Si:V 2 + , Si:V 2 0 , Si:V 2 - ), of the oxygen pair (Si:O 2 ) and the oxygen-vacancy pair (Si:O.V) neighbours in the silicon lattice, is studied. Distortions for the symmetry were included in the Si:V 2 + and Si:O 2 systems. The behavior of defect levels related to the cluster size of Si:V 2 0 and Si:O 2 systems, the insulated oxygen impurity of silicon in interstitial position (Si:O i ), and the complexes involving four oxygen atoms are analysed. (M.C.K.) [pt

The effect of gold nanoparticles on exchange processes in collision complexes of triplet and singlet oxygen molecules with excited eosin molecules

Science.gov (United States)

Bryukhanov, V. V.; Minaev, B. M.; Tsibul'nikova, A. V.; Slezhkin, V. A.

2015-07-01

We have studied exchange processes in contact complexes of triplet eosin molecules with oxygen molecules in the triplet (3Σ{/g -}) and singlet (1Δ g ) states in thin polyvinylbutyral films in the presence of gold nanoparticles. Upon resonant excitation of surface plasmons in gold nanoparticles into the absorption band of eosin molecules-singlet oxygen sensitizers-we have obtained an increase in the intensity of the delayed fluorescence and an increase in the lifetime of the dye with simultaneous quenching of the luminescence of singlet oxygen. The kinetics of the delayed fluorescence of the dye as a result of singlet-triplet annihilation of triplet eosin molecules with singlet oxygen molecules has been investigated. To compare theoretical and experimental data, we have numerically simulated energy transfer processes. Rate constants of energy transfer and of singlet-triplet annihilation, as well as quenching constants of triplet states of the dye by molecular oxygen, have been calculated. Luminescence quantum yield 1Δ g of polyvinylbutyral has been estimated. We have analyzed quantum-chemically electronic mechanisms of singlet-triplet annihilation of oxygen and eosin.

Origin of photosynthetic oxygen

International Nuclear Information System (INIS)

Gerster, Richard; Dupuy, Jacques; Guerin de Montgareuil, Pierre

From the comparison of isotopic exchange kinetics between C 18 O 2 and the water of algae suspensions or aerial leaves subjected to alternating darkness and light, it becomes possible to calculate the isotopic abundance of the CO 2 involved in the photochemical process; this value has been compared to those of the intracellular water and of the evolved O 2 . Kinetics of the appearance of 18 O in the oxygen produced by algae suspended in enriched water are also presented [fr

Quantitative Analysis of Oxygen Gas Exhausted from Anode through In Situ Measurement during Electrolytic Reduction

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2017-01-01

Full Text Available Quantitative analysis by in situ measurement of oxygen gas evolved from an anode was employed to monitor the progress of electrolytic reduction of simulated oxide fuel in a molten Li2O–LiCl salt. The electrolytic reduction of 0.6 kg of simulated oxide fuel was performed in 5 kg of 1.5 wt.% Li2O–LiCl molten salt at 650°C. Porous cylindrical pellets of simulated oxide fuel were used as the cathode by loading a stainless steel wire mesh cathode basket. A platinum plate was employed as the anode. The oxygen gas evolved from the anode was exhausted to the instrumentation for in situ measurement during electrolytic reduction. The instrumentation consisted of a mass flow controller, pump, wet gas meter, and oxygen gas sensor. The oxygen gas was successfully measured using the instrumentation in real time. The measured volume of the oxygen gas was comparable to the theoretically calculated volume generated by the charge applied to the simulated oxide fuel.

Evolvable synthetic neural system

Science.gov (United States)

Curtis, Steven A. (Inventor)

2009-01-01

An evolvable synthetic neural system includes an evolvable neural interface operably coupled to at least one neural basis function. Each neural basis function includes an evolvable neural interface operably coupled to a heuristic neural system to perform high-level functions and an autonomic neural system to perform low-level functions. In some embodiments, the evolvable synthetic neural system is operably coupled to one or more evolvable synthetic neural systems in a hierarchy.

Biomimetic molecular design tools that learn, evolve, and adapt

Science.gov (United States)

2017-01-01

A dominant hallmark of living systems is their ability to adapt to changes in the environment by learning and evolving. Nature does this so superbly that intensive research efforts are now attempting to mimic biological processes. Initially this biomimicry involved developing synthetic methods to generate complex bioactive natural products. Recent work is attempting to understand how molecular machines operate so their principles can be copied, and learning how to employ biomimetic evolution and learning methods to solve complex problems in science, medicine and engineering. Automation, robotics, artificial intelligence, and evolutionary algorithms are now converging to generate what might broadly be called in silico-based adaptive evolution of materials. These methods are being applied to organic chemistry to systematize reactions, create synthesis robots to carry out unit operations, and to devise closed loop flow self-optimizing chemical synthesis systems. Most scientific innovations and technologies pass through the well-known “S curve”, with slow beginning, an almost exponential growth in capability, and a stable applications period. Adaptive, evolving, machine learning-based molecular design and optimization methods are approaching the period of very rapid growth and their impact is already being described as potentially disruptive. This paper describes new developments in biomimetic adaptive, evolving, learning computational molecular design methods and their potential impacts in chemistry, engineering, and medicine. PMID:28694872

Biomimetic molecular design tools that learn, evolve, and adapt

Directory of Open Access Journals (Sweden)

David A Winkler

2017-06-01

Full Text Available A dominant hallmark of living systems is their ability to adapt to changes in the environment by learning and evolving. Nature does this so superbly that intensive research efforts are now attempting to mimic biological processes. Initially this biomimicry involved developing synthetic methods to generate complex bioactive natural products. Recent work is attempting to understand how molecular machines operate so their principles can be copied, and learning how to employ biomimetic evolution and learning methods to solve complex problems in science, medicine and engineering. Automation, robotics, artificial intelligence, and evolutionary algorithms are now converging to generate what might broadly be called in silico-based adaptive evolution of materials. These methods are being applied to organic chemistry to systematize reactions, create synthesis robots to carry out unit operations, and to devise closed loop flow self-optimizing chemical synthesis systems. Most scientific innovations and technologies pass through the well-known “S curve”, with slow beginning, an almost exponential growth in capability, and a stable applications period. Adaptive, evolving, machine learning-based molecular design and optimization methods are approaching the period of very rapid growth and their impact is already being described as potentially disruptive. This paper describes new developments in biomimetic adaptive, evolving, learning computational molecular design methods and their potential impacts in chemistry, engineering, and medicine.

Complexity of low-frequency blood oxygen level-dependent fluctuations covaries with local connectivity.

Science.gov (United States)

Anderson, Jeffrey S; Zielinski, Brandon A; Nielsen, Jared A; Ferguson, Michael A

2014-04-01

Very low-frequency blood oxygen level-dependent (BOLD) fluctuations have emerged as a valuable tool for describing brain anatomy, neuropathology, and development. Such fluctuations exhibit power law frequency dynamics, with largest amplitude at lowest frequencies. The biophysical mechanisms generating such fluctuations are poorly understood. Using publicly available data from 1,019 subjects of age 7-30, we show that BOLD fluctuations exhibit temporal complexity that is linearly related to local connectivity (regional homogeneity), consistently and significantly covarying across subjects and across gray matter regions. This relationship persisted independently of covariance with gray matter density or standard deviation of BOLD signal. During late neurodevelopment, BOLD fluctuations were unchanged with age in association cortex while becoming more random throughout the rest of the brain. These data suggest that local interconnectivity may play a key role in establishing the complexity of low-frequency BOLD fluctuations underlying functional magnetic resonance imaging connectivity. Stable low-frequency power dynamics may emerge through segmentation and integration of connectivity during development of distributed large-scale brain networks. Copyright © 2013 Wiley Periodicals, Inc.

Evolving Microbial Communities in Cellulose-Fed Microbial Fuel Cell

Directory of Open Access Journals (Sweden)

Renata Toczyłowska-Mamińska

2018-01-01

Full Text Available The abundance of cellulosic wastes make them attractive source of energy for producing electricity in microbial fuel cells (MFCs. However, electricity production from cellulose requires obligate anaerobes that can degrade cellulose and transfer electrons to the electrode (exoelectrogens, and thus most previous MFC studies have been conducted using two-chamber systems to avoid oxygen contamination of the anode. Single-chamber, air-cathode MFCs typically produce higher power densities than aqueous catholyte MFCs and avoid energy input for the cathodic reaction. To better understand the bacterial communities that evolve in single-chamber air-cathode MFCs fed cellulose, we examined the changes in the bacterial consortium in an MFC fed cellulose over time. The most predominant bacteria shown to be capable electron generation was Firmicutes, with the fermenters decomposing cellulose Bacteroidetes. The main genera developed after extended operation of the cellulose-fed MFC were cellulolytic strains, fermenters and electrogens that included: Parabacteroides, Proteiniphilum, Catonella and Clostridium. These results demonstrate that different communities evolve in air-cathode MFCs fed cellulose than the previous two-chamber reactors.

Life: Complexity and Diversity

Indian Academy of Sciences (India)

tinual increase in the diversity of life over evolutionary time. Ways of ... Centre for Ecological. Scienc'es .... plants evolved flowers to attract pollinators and reward them with .... with the evolving complexity of their interactions in communi- ties.

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

Czech Academy of Sciences Publication Activity Database

Lee, S.M.; Hrma, P.; Kloužek, Jaroslav; Pokorný, R.; Hujová, Miroslava; Dixon, D.R.; Schweiger, M. J.; Kruger, A.A.

2017-01-01

Roč. 43, č. 16 (2017), s. 13113-13118 ISSN 0272-8842 Institutional support: RVO:67985891 Keywords : oxygen mass balance * feed-to-glass conversion * evolved gas * oxygen partial pressure * Fe redox ratio Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 2.986, year: 2016

Complexity Theory

Science.gov (United States)

Lee, William H K.

2016-01-01

A complex system consists of many interacting parts, generates new collective behavior through self organization, and adaptively evolves through time. Many theories have been developed to study complex systems, including chaos, fractals, cellular automata, self organization, stochastic processes, turbulence, and genetic algorithms.

X-ray induced inactivation of the capacity for photosynthetic oxygen evolution and nitrate reduction in blue-green algae

International Nuclear Information System (INIS)

Stevens, S.E. Jr.; Simic, M.G.; Rao, V.S.K.

1975-01-01

The level of inactivation of oxygen evolving photosynthesis in the green alga, Chlorella pyrenoidosa was 12 percent in N 2 at a dose of 100 krad of x irradiation. Under similar conditions, as well as under O 2 , there resulted a 20 percent inactivation of the same function in the blue-green algae, Agmenellum quadruplicatum, strains PR-6 and AQ-6. Nitrate reduction capacity in the mutant AQ-6 was inactivated to 40 percent in N 2 and to 7 percent in O 2 . Catalase and formate provided some protection from irradiation in O 2 , suggesting some inactivation by H 2 O 2 . Most of the damage to the nitrate reduction system resulted from the direct action of x irradiation on a constitutive subunit of the nitrate reductase complex. Moreover, the slight inactivation of the O 2 evolving system, a function which is associated with photosystem II, cannot account for the inactivation of nitrate reduction

Why, when and where did honey bee dance communication evolve?

Directory of Open Access Journals (Sweden)

Robbie eI'Anson Price

2015-11-01

Full Text Available Honey bees (Apis sp. are the only known bee genus that uses nest-based communication to provide nest-mates with information about the location of resources, the so-called dance language. Successful foragers perform waggle dances for high quality food sources and suitable nest-sites during swarming. However, since many species of social insects do not communicate the location of resources to their nest-mates, the question of why the dance language evolved is of ongoing interest. We review recent theoretical and empirical research into the ecological circumstances that make dance communication beneficial in present day environments. This research suggests that the dance language is most beneficial when food sources differ greatly in quality and are hard to find. The dances of extant honey bee species differ in important ways, and phylogenetic studies suggest an increase in dance complexity over time: species with the least complex dance were the first to appear and species with the most complex dance are the most derived. We review the fossil record of honey bees and speculate about the time and context (foraging vs. swarming in which spatially referential dance communication might have evolved. We conclude that there are few certainties about when the dance language first appeared; dance communication could be older than 40 million years and, thus, predate the genus Apis, or it could be as recent as 20 million years when extant honey bee species diverged during the early Miocene. The most parsimonious scenario assumes it evolved in a sub-tropical to temperate climate, with patchy vegetation somewhere in Eurasia.

Maintaining evolvability.

Science.gov (United States)

Crow, James F

2008-12-01

is yet to be determined. It is likely that only a case-by-case analysis will provide the answers. Despite the difficulties that complex interactions cause for evolution in Mendelian populations, such populations nevertheless evolve very well. Longlasting species must have evolved mechanisms for coping with such problems. Since such difficulties do not arise in asexual populations, a comparison of epistatic patterns in closely related sexual and asexual species might provide some important insights.

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.

Science.gov (United States)

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.

Evolvable mathematical models: A new artificial Intelligence paradigm

Science.gov (United States)

Grouchy, Paul

We develop a novel Artificial Intelligence paradigm to generate autonomously artificial agents as mathematical models of behaviour. Agent/environment inputs are mapped to agent outputs via equation trees which are evolved in a manner similar to Symbolic Regression in Genetic Programming. Equations are comprised of only the four basic mathematical operators, addition, subtraction, multiplication and division, as well as input and output variables and constants. From these operations, equations can be constructed that approximate any analytic function. These Evolvable Mathematical Models (EMMs) are tested and compared to their Artificial Neural Network (ANN) counterparts on two benchmarking tasks: the double-pole balancing without velocity information benchmark and the challenging discrete Double-T Maze experiments with homing. The results from these experiments show that EMMs are capable of solving tasks typically solved by ANNs, and that they have the ability to produce agents that demonstrate learning behaviours. To further explore the capabilities of EMMs, as well as to investigate the evolutionary origins of communication, we develop NoiseWorld, an Artificial Life simulation in which interagent communication emerges and evolves from initially noncommunicating EMM-based agents. Agents develop the capability to transmit their x and y position information over a one-dimensional channel via a complex, dialogue-based communication scheme. These evolved communication schemes are analyzed and their evolutionary trajectories examined, yielding significant insight into the emergence and subsequent evolution of cooperative communication. Evolved agents from NoiseWorld are successfully transferred onto physical robots, demonstrating the transferability of EMM-based AIs from simulation into physical reality.

Modelling the effects of oxygen evolution in the all-vanadium redox flow battery

International Nuclear Information System (INIS)

Al-Fetlawi, H.; Shah, A.A.; Walsh, F.C.

2010-01-01

The impact of oxygen evolution and bubble formation on the performance of an all-vanadium redox flow battery is investigated using a two-dimensional, non-isothermal model. The model is based on mass, charge, energy and momentum conservation, together with a kinetic model for the redox and gas-evolving reactions. The multi-phase mixture model is used to describe the transport of oxygen in the form of gas bubbles. Numerical simulations are compared to experimental data, demonstrating good agreement. Parametric studies are performed to investigate the effects of changes in the operating temperature, electrolyte flow rate and bubble diameter on the extent of oxygen evolution. Increasing the electrolyte flow rate is found to reduce the volume of the oxygen gas evolved in the positive electrode. A larger bubble diameter is demonstrated to increase the buoyancy force exerted on the bubbles, leading to a faster slip velocity and a lower gas volume fraction. Substantial changes are observed over the range of reported bubble diameters. Increasing the operating temperature was found to increase the gas volume as a result of the enhanced rate of O 2 evolution. The charge efficiency of the cell drops markedly as a consequence.

Cis-Lunar Reusable In-Space Transportation Architecture for the Evolvable Mars Campaign

Science.gov (United States)

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.

Effects of Different Sera Conditions on Olfactory Ensheathing Cells in Vitro

Directory of Open Access Journals (Sweden)

Meng Lu

2014-12-01

Full Text Available Transplantation of olfactory ensheathing cells (OEC is a promising therapy in spinal cord injury (SCI treatment. However, the therapeutic efficacy of this method is unstable due to unknown reasons. Considering the alterations in the culture environment that occur during OEC preparation for transplantation, we hypothesize that these changes may cause variations in the curative effects of this method. In this study, we compared OEC cultured in medium containing different types and concentrations of serum. After purification and passage, the OEC were cultured for 7 days in different media containing 5%, 10%, 15% or 20% fetal bovine serum (FBS or rat serum (RS, or the cells were cultured in FBS-containing medium first, followed by medium containing RS. In another group, the OEC were first cultured in 10% FBS for 3 days and then cultured with rat spinal cord explants with 10% RS for another 4 days. An MTT assay and P75 neurotrophin receptor immunofluorescence staining were used to examine cell viability and OEC numbers, respectively. The concentration of neurotrophin-3 (NT-3, which is secreted by OEC into the culture supernatant, was detected using the enzyme-linked immunosorbent assay (ELISA. RT-PCR was applied to investigate the NT-3 gene expression in OEC according to different groups. Compared with FBS, RS reduced OEC proliferation in relation to OEC counts (χ2 = 166.279, df = 1, p < 0.01, the optical density (OD value in the MTT assay (χ2 = 34.730, df = 1, p < 0.01, and NT-3 concentration in the supernatant (χ2 = 242.997, df = 1, p < 0.01. OEC cultured with spinal cord explants secreted less NT-3 than OEC cultured alone (F = 9.611, df = 5.139, p < 0.01. Meanwhile, the order of application of different sera was not influential. There was statistically significant difference in NT-3 gene expression among different groups when the serum concentration was 15% (χ2 = 64.347, df = 1, p < 0.01. In conclusion, different serum conditions may be

Singlet oxygen generator for a solar powered chemically pumped iodine laser

Science.gov (United States)

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.

NADPH oxidase complex-derived reactive oxygen species, the actin cytoskeleton, and rho GTPases in cell migration

DEFF Research Database (Denmark)

Stanley, Alanna; Thompson, Kerry; Hynes, Ailish

2014-01-01

Abstract Significance: Rho GTPases are historically known to be central regulators of actin cytoskeleton reorganization. This affects many processes including cell migration. In addition, members of the Rac subfamily are known to be involved in reactive oxygen species (ROS) production through...... mediating cytoskeletal reorganization. Critical Issues: The role of the actin cytoskeleton in providing a scaffold for components of the Nox complex needs to be examined in the light of these new advances. During cell migration, Rho GTPases, ROS, and cytoskeletal organization appear to function as a complex...... compartments. This in conjunction with the analysis of tissues lacking specific Rho GTPases, and Nox components will facilitate a detailed examination of the interactions of these structures with the actin cytoskeleton. In combination with the analysis of ROS production, including its subcellular location...

Evolved stars as complex chemical laboratories - the quest for gaseous chemistry

Science.gov (United States)

Katrien Els Decin, Leen

2015-08-01

At the end of their life, most stars lose a large fraction of their mass through a stellar wind. The stellar winds of evolved (super)giant stars are the dominant suppliers for the pristine building blocks of the interstellar medium (ISM). Crucial to the understanding of the chemical life cycle of the ISM is hence a profound insight in the chemical and physical structure governing these stellar winds.These winds are really unique chemical laboratories in which currently more than 70 different molecules and 15 different dust species are detected. Several chemical processes such as neutral-neutral and ion-molecule gas-phase reactions, dust nucleation and growth, and photo-processes determine the chemical content of these winds. However, gas-phase and dust-nucleation chemistry for astronomical environments still faces many challenges. One should realize that only ˜15% of the rate coefficients for gas-phase reactions considered to occur in (inter/circum)stellar regions at temperatures (T) below 300K have been subject to direct laboratory determinations and that the temperature dependence of the rate constants is often not known; only ˜2% have rate constants at Tgrant, we are now in the position to solve some riddles involved in understanding the gas-phase chemistry in evolved stars. In this presentation, I will demonstrate the need for accurate temperature-dependent gas-phase reaction rate constants and will present our new laboratory equipment built to measure the rate constants for species key in stellar wind chemistry. Specifically, we aim to obtain the rate constants of reactions involving silicon- and sulphur bearing species and HCCO for 30

Reduced Moment-Based Models for Oxygen Precipitates and Dislocation Loops in Silicon

Science.gov (United States)

Trzynadlowski, Bart

The demand for ever smaller, higher-performance integrated circuits and more efficient, cost-effective solar cells continues to push the frontiers of process technology. Fabrication of silicon devices requires extremely precise control of impurities and crystallographic defects. Failure to do so not only reduces performance, efficiency, and yield, it threatens the very survival of commercial enterprises in today's fiercely competitive and price-sensitive global market. The presence of oxygen in silicon is an unavoidable consequence of the Czochralski process, which remains the most popular method for large-scale production of single-crystal silicon. Oxygen precipitates that form during thermal processing cause distortion of the surrounding silicon lattice and can lead to the formation of dislocation loops. Localized deformation caused by both of these defects introduces potential wells that trap diffusing impurities such as metal atoms, which is highly desirable if done far away from sensitive device regions. Unfortunately, dislocations also reduce the mechanical strength of silicon, which can cause wafer warpage and breakage. Engineers must negotiate this and other complex tradeoffs when designing fabrication processes. Accomplishing this in a complex, modern process involving a large number of thermal steps is impossible without the aid of computational models. In this dissertation, new models for oxygen precipitation and dislocation loop evolution are described. An oxygen model using kinetic rate equations to evolve the complete precipitate size distribution was developed first. This was then used to create a reduced model tracking only the moments of the size distribution. The moment-based model was found to run significantly faster than its full counterpart while accurately capturing the evolution of oxygen precipitates. The reduced model was fitted to experimental data and a sensitivity analysis was performed to assess the robustness of the results. Source

Heterologous Expression of Moss Light-harvesting Complex Stress-related 1 (LHCSR1), the Chlorophyll a-Xanthophyll Pigment-protein Complex Catalyzing Non-photochemical Quenching, in Nicotiana sp.*

Science.gov (United States)

Pinnola, Alberta; Ghin, Leonardo; Gecchele, Elisa; Merlin, Matilde; Alboresi, Alessandro; Avesani, Linda; Pezzotti, Mario; Capaldi, Stefano; Cazzaniga, Stefano; Bassi, Roberto

2015-01-01

Oxygenic photosynthetic organisms evolved mechanisms for thermal dissipation of energy absorbed in excess to prevent formation of reactive oxygen species. The major and fastest component, called non-photochemical quenching, occurs within the photosystem II antenna system by the action of two essential light-harvesting complex (LHC)-like proteins, photosystem II subunit S (PSBS) in plants and light-harvesting complex stress-related (LHCSR) in green algae and diatoms. In the evolutionary intermediate Physcomitrella patens, a moss, both gene products are active. These proteins, which are present in low amounts, are difficult to purify, preventing structural and functional analysis. Here, we report on the overexpression of the LHCSR1 protein from P. patens in the heterologous systems Nicotiana benthamiana and Nicotiana tabacum using transient and stable nuclear transformation. We show that the protein accumulated in both heterologous systems is in its mature form, localizes in the chloroplast thylakoid membranes, and is correctly folded with chlorophyll a and xanthophylls but without chlorophyll b, an essential chromophore for plants and algal LHC proteins. Finally, we show that recombinant LHCSR1 is active in quenching in vivo, implying that the recombinant protein obtained is a good material for future structural and functional studies. PMID:26260788

Compound C prevents Hypoxia-Inducible Factor-1α protein stabilization by regulating the cellular oxygen availability via interaction with Mitochondrial Complex I

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Hagen Thilo

2011-04-01

Full Text Available Abstract The transcription factor Hypoxia-Inducible Factor-1α is a master regulator of the cellular response to low oxygen concentration. Compound C, an inhibitor of AMP-activated kinase, has been reported to inhibit hypoxia dependent Hypoxia-Inducible Factor-1α activation via a mechanism that is independent of AMP-activated kinase but dependent on its interaction with the mitochondrial electron transport chain. The objective of this study is to characterize the interaction of Compound C with the mitochondrial electron transport chain and to determine the mechanism through which the drug influences the stability of the Hypoxia-Inducible Factor-1α protein. We found that Compound C functions as an inhibitor of complex I of the mitochondrial electron transport chain as demonstrated by its effect on mitochondrial respiration. It also prevents hypoxia-induced Hypoxia-Inducible Factor-1α stabilization in a dose dependent manner. In addition, Compound C does not have significant effects on reactive oxygen species production from complex I via both forward and reverse electron flux. This study provides evidence that similar to other mitochondrial electron transport chain inhibitors, Compound C regulates Hypoxia-Inducible Factor-1α stability by controlling the cellular oxygen concentration.

GC/MS Analysis of Oil Extractives from Wood and Bark of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua

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Mohamed Zidan Mohamed Salem

2015-09-01

Full Text Available Wood and bark oil extractives components (OECs of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua grown in the Czech Republic were analyzed using gas chromatography/ mass spectrometry (GC/MS. The analysis showed the presence of monoterpene, sesquiterpene, diterpenoids, and resin acids. The highest percentages of OECs in the wood of P. sylvestris were α-fenchyl alcohol (26.04%, D-fenchyl alcohol (12.39%, and L-borneol (8.81%; the OECs in the bark included α-methyl-γ-butyrolactone (31.88% and isodecyl octyl phthalate (15.85%. The most frequently occurring OEC in A. alba wood were 4-hydroxy-4-methyl-2-pentanone (73.36%, α-cedrol (10.08%, and 2,6-dimethyl-1,3,6-heptatriene (7.35%; the most OECs in the bark were di(2-ethylhexylphthalate (59.83%, methyl cyclopentane (16.63%, and 13-epimanool (6.31%. P. abies wood OECs included 4-hydroxy-4-methyl-2-pentanone (29.42%, α-cedrol (26.98%, ∆3-carene (6.08%, and terpinen-4-ol (5.42%; the most OECs in the bark were di(2-ethylhexylphthalate (30.91%, cyclohexane (12.89%, caryophyllene oxide (8.90%, and α-pinene (4.59%. OECs of L. decidua wood were α-terpineol (26.06%, isoborneol (14.12%, camphene (11.78%, D-fenchyl alcohol (10.39%, and larixol (4.85%; OECs in the bark were larixol (33.29%, phthalic acid mono-2-ethylhexyl ester (16.96%, 13-epimanool (15.40%, and cyclohexane (8.44%.

Earth’s oxygen cycle and the evolution of animal life

Science.gov (United States)

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

Evolving approaches to the ethical management of genomic data.

Science.gov (United States)

McEwen, Jean E; Boyer, Joy T; Sun, Kathie Y

2013-06-01

The ethical landscape in the field of genomics is rapidly shifting. Plummeting sequencing costs, along with ongoing advances in bioinformatics, now make it possible to generate an enormous volume of genomic data about vast numbers of people. The informational richness, complexity, and frequently uncertain meaning of these data, coupled with evolving norms surrounding the sharing of data and samples and persistent privacy concerns, have generated a range of approaches to the ethical management of genomic information. As calls increase for the expanded use of broad or even open consent, and as controversy grows about how best to handle incidental genomic findings, these approaches, informed by normative analysis and empirical data, will continue to evolve alongside the science. Published by Elsevier Ltd.

Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a MnV–Oxo Complex

Science.gov (United States)

Neu, Heather M; Quesne, Matthew G; Yang, Tzuhsiung; Prokop-Prigge, Katharine A; Lancaster, Kyle M; Donohoe, James; DeBeer, Serena; de Visser, Sam P; Goldberg, David P

2014-01-01

Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [MnV(O)(TBP8Cz)(CN)]− was generated from addition of Bu4N+CN− to the 5-coordinate MnV(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives Mn–O=1.53 Å, Mn–CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN− complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e−-reduced MnIII(CN)− complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol−1, ΔS≠=−10 cal mol−1 K−1. Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate MnV(O) complexes. PMID:25256417

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films

Energy Technology Data Exchange (ETDEWEB)

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.

2017-01-30

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.

Local cerebral blood flow (1CBF) and oxygen consumption (1CMRO2) in evolving irreversible ischemic infarction: a study with positron tomography and oxygen-15

International Nuclear Information System (INIS)

Baron, J.C.; Rougemont, D.; Lebrun-Grandie, P.; Comar, D.; Bousser, M.G.; Bories, J.; Castaigne, P.; Cabanis, E.

1982-09-01

In 25 patients suffering from cerebral ischemia set up in the area of the internal carotid artery the local cerebral blood flow (lCBF) and local cerebral oxygen consumption (lCMRO 2 ) were measured by the method of continuous inhalation of oxygen 15-labelled gas combined with positron emission tomography. These two local parameters and their ratio, the local oxygen extraction rate (lO 2 E), were studied inside the brain region tending spontaneously towards ischemic necrosis, a zone defined by means of repeated tomodensitometric examinations. The essential facts observed are the variability of the lCBF and the lO 2 E values, from extremely low to extremely high, whereas the collapse of the lCMRO 2 is constant. Consequently this last parameter alone would be a good prognostic index, an lCMRO 2 decrease to a level below about 70% of the controlateral value indicating that the necrosis is spontaneously irreparable. These results are discussed in the light of published data

Roles of Neuroglobin Binding to Mitochondrial Complex III Subunit Cytochrome c1 in Oxygen-Glucose Deprivation-Induced Neurotoxicity in Primary Neurons.

Science.gov (United States)

Yu, Zhanyang; Zhang, Yu; Liu, Ning; Yuan, Jing; Lin, Li; Zhuge, Qichuan; Xiao, Jian; Wang, Xiaoying

2016-07-01

Neuroglobin (Ngb) is a tissue globin specifically expressed in brain neurons. Recent studies by our laboratory and others have demonstrated that Ngb is protective against stroke and related neurological disorders, but the mechanisms remain poorly understood. We previously identified cytochrome c1 (Cyc1) as an Ngb-interacting molecule by yeast two-hybrid screening. Cyc1 is a subunit of mitochondria complex III, which is a component of mitochondrial respiratory chain and a major source of reactive oxygen species (ROS) production under both physiological and pathological conditions. In this study, we for the first time defined Ngb-Cyc1 binding, and investigated its roles in oxygen-glucose deprivation (OGD)/reoxygenation-induced neurotoxicity and ROS production in primary neurons. Immunocytochemistry and co-immunoprecipitation validated Ngb-Cyc1 binding, which was significantly increased by OGD and Ngb overexpression. We found 4 h OGD with/without 4 h reoxygenation significantly increased complex III activity, but this activity elevation was significantly attenuated in three groups of neurons: Ngb overexpression, specific complex III inhibitor stigmatellin, or stigmatellin plus Ngb overexpression, whereas there was no significant differences between these three groups, suggesting Ngb-Cyc1 binding may function in suppressing OGD-mediated complex III activity elevation. Importantly, these three groups of neurons also showed significant decreases in OGD-induced superoxide anion generation and neurotoxicity. These results suggest that Ngb can bind to mitochondrial complex III subunit Cyc1, leading to suppression of OGD-mediated complex III activity and subsequent ROS production elevation, and eventually reduction of OGD-induced neurotoxicity. This molecular signaling cascade may be at least part of the mechanisms of Ngb neuroprotection against OGD-induced neurotoxicity.

Money Laundering Detection Framework to Link the Disparate and Evolving Schemes

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Murad Mehmet

2013-09-01

Full Text Available Money launderers hide traces of their transactions with the involvement of entities that participate in sophisticated schemes. Money laundering detection requires unraveling concealed connections among multiple but seemingly unrelated human money laundering networks, ties among actors of those schemes, and amounts of funds transferred among those entities. The link among small networks, either financial or social, is the primary factor that facilitates money laundering. Hence, the analysis of relations among money laundering networks is required to present the full structure of complex schemes. We propose a framework that uses sequence matching, case-based analysis, social network analysis, and complex event processing to detect money laundering. Our framework captures an ongoing single scheme as an event, and associations among such ongoing sequence of events to capture complex relationships among evolving money laundering schemes. The framework can detect associated multiple money laundering networks even in the absence of some evidence. We validated the accuracy of detecting evolving money laundering schemes using a multi-phases test methodology. Our test used data generated from real-life cases, and extrapolated to generate more data from real-life schemes generator that we implemented.

Efficient and selective singlet oxygen sensitized NIR luminescence of a neodymium(III) complex and its application in biological imaging

Energy Technology Data Exchange (ETDEWEB)

Lo, Wai-Sum [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Li, Hongguang [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Law, Ga-Lai, E-mail: ga-lai.law@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak, E-mail: bcwtwong@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

2016-01-15

A responsive neodymium NIR emission ({sup 4}F{sub 3/2}→{sup 4}I{sub 11/2,} {sub 9/2}) was recorded upon binding with singlet oxygen (K{sub B}=1.79×10{sup 6} M{sup −1}) via the anthracene moiety. The motif ytterbium analog served as a negative control with no significant NIR enhancement/quenching with the addition of the same amount of singlet oxygen. Our complex was also found to react with {sup 1}O{sub 2} generated by a known photosensitizer TMPyP inside HeLa cells without inducing cell death and display no significant cytotoxicity. - Highlights: • A turn-on NIR-emissive {sup 1}O{sub 2} probe has been synthesized for potential biological applications. • It has a binding constant of 1.9×10{sup 6} M{sup −1} and the emission intensity has a 5-fold increase upon binding. • The probe was also found to quench singlet oxygen in vitro generated by known photosensitizer TMPyP.

Improved Neural Regeneration with Olfactory Ensheathing Cell Inoculated PLGA Scaffolds in Spinal Cord Injury Adult Rats

Directory of Open Access Journals (Sweden)

Changxing Wang

2017-03-01

Full Text Available Background/Aims: Every year, around the world, between 250000 and 500000 people suffer from spinal cord injury (SCI. This study investigated the potential for poly (lactic-co-glycolic acid (PLGA complex inoculated with olfactory ensheathing cells (OECs to treat spinal cord injury in a rat model. Methods: OECs were identified by immunofluorescence based on the nerve growth factor receptor (NGFR p75. The Basso, Beattie, and Bresnahan (BBB score, together with an inclined plane (IP test were used to detect functional recovery. Nissl staining along with the luxol fast blue (LFB staining were independently employed to illustrate morphological alterations. More so, immunofluorescence labeling of the glial fibrillary acidic protein (GFAP and the microtubule-associated protein-2 (MAP-2, representing astrocytes and neurons respectively, were investigated at time points of weeks 2 and 8 post-operation. Results: The findings showed enhanced locomotor recovery, axon myelination and better protected neurons post SCI when compared with either PLGA or untreated groups (P < 0.05. Conclusion: PLGA complexes inoculated with OECs improve locomotor functional recovery in transected spinal cord injured rat models, which is most likely due to the fact it is conducive to a relatively benevolent microenvironment, has nerve protective effects, as well as the ability to enhance remyelination, via a promotion of cell differentiation and inhibition of astrocyte formation.

Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

International Nuclear Information System (INIS)

Kelley, D.

1990-01-01

The kinetics of the reactions of C 2 H 5 radical with Co(NH 3 ) 5 X 2+ , Ru(NH 3 ) 5 X 2+ , and Co(dmgH) 2 (X) (Y) (X = Br, Cl, N 3 , SCN; Y = H 2 O, CH 3 CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with β-Ni(cyclam) 2+ were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ were studied. Activation parameters were obtained for the unimolecular homolysis of C 2 H 5 Ni(cyclam)H 2 O 2+ . Kinetic and thermodynamic data obtained from these reactions were compared with those for the σ-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ complexes were studied by monitoring the formation of the oxygen insertion product RO 2 Ni(cyclam)H 2 O 2+ . The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs

Species-specific control of cellular proliferation and the impact of large animal models for the use of olfactory ensheathing cells and Schwann cells in spinal cord repair.

Science.gov (United States)

Wewetzer, Konstantin; Radtke, Christine; Kocsis, Jeffery; Baumgärtner, Wolfgang

2011-05-01

Autologous transplantation of olfactory ensheathing cells (OECs) and Schwann cells (SCs) is considered a promising option to promote axonal regrowth and remyelination after spinal cord injury in humans. However, if the experimental data from the rodent model can be directly extrapolated to humans, as widely believed, remains to be established. While limitations of the rodent system have recently been discussed with regard to the distinct organization of the motor systems, the question whether OECs and SCs may display species-specific properties has not been fully addressed. Prompted by recent studies on canine and porcine glia, we performed a detailed analysis of the in vitro and in vivo properties of OECs and SCs and show that rodent but not human, monkey, porcine, and canine glia require mitogens for in vitro expansion, display a complex response to elevated intracellular cAMP, and undergo spontaneous immortalization upon prolonged mitogen stimulation. These data indicate fundamental inter-species differences of the control of cellular proliferation. Whether OECs and SCs from large animals and humans share growth-promoting in vivo properties with their rodent counterpart is not yet clear. Autologous implantation studies in humans did not reveal adverse effects of cell transplantation so far. However, in vivo studies of large animal or human glia and rodent recipients mainly focused on the remyelinating potential of the transplanted cells. Thus, further experimental in vivo studies in large animals are essential to fully define the axonal growth-promoting potential of OECs and SCs. Based on the homology of the in vitro growth control between porcine, canine and human glia, it is concluded that these species may serve as valuable translational models for scaling up human procedures. This article is part of a Special Issue entitled: Understanding olfactory ensheathing glia and their prospect for nervous system repair. Copyright © 2010 Elsevier Inc. All rights

Robustness to Faults Promotes Evolvability: Insights from Evolving Digital Circuits.

Science.gov (United States)

Milano, Nicola; Nolfi, Stefano

2016-01-01

We demonstrate how the need to cope with operational faults enables evolving circuits to find more fit solutions. The analysis of the results obtained in different experimental conditions indicates that, in absence of faults, evolution tends to select circuits that are small and have low phenotypic variability and evolvability. The need to face operation faults, instead, drives evolution toward the selection of larger circuits that are truly robust with respect to genetic variations and that have a greater level of phenotypic variability and evolvability. Overall our results indicate that the need to cope with operation faults leads to the selection of circuits that have a greater probability to generate better circuits as a result of genetic variation with respect to a control condition in which circuits are not subjected to faults.

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

Science.gov (United States)

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Mitochondria Targetable Time-Gated Luminescence Probe for Singlet Oxygen Based on a β-Diketonate-Europium Complex.

Science.gov (United States)

Sun, Jingyan; Song, Bo; Ye, Zhiqiang; Yuan, Jingli

2015-12-21

Singlet oxygen ((1)O2) plays a key role in the photodynamic therapy (PDT) technique of neoplastic diseases. In this work, by using a 9,10-dimethyl-2-anthryl-containing β-diketone, 1,1,1,2,2-pentafluoro-5-(9',10'-dimethyl-2'-anthryl)-3,5-pentanedione (Hpfdap), as a (1)O2-recognition ligand, a novel β-diketonate-europium(III) complex that can act as a luminescence probe for (1)O2, [Eu(pfdap)3(tpy)] (tpy = 2,2',2″-terpyridine), has been designed and synthesized for the time-gated luminescence detection of (1)O2 in living cells. The complex is weakly luminescent due to the quenching effect of 9,10-dimethyl-2-anthryl groups. After reaction with (1)O2, accompanied by the formation of endoperoxides of 9,10-dimethyl-2-anthryl groups, the luminescence quenching disappears, so that the long-lived luminescence of the europium(III) complex is switched on. The complex showed highly selective luminescence response to (1)O2 with a remarkable luminescence enhancement. Combined with the time-gated luminescence imaging technique, the complex was successfully used as a luminescent probe for the monitoring of the time-dependent generation of (1)O2 in 5-aminolevulinic acid (a PDT drug) loaded HepG2 cells during the photodynamic process. In addition, by coloading the complex and a mitochondrial indicator, Mito-Tracker Green, into HepG2 cells, the specific localization of [Eu(pfdap)3(tpy)] molecules in mitochondria of HepG2 cells was demonstrated by confocal fluorescence imaging measurements.

Preface: evolving rotifers, evolving science: Proceedings of the XIV International Rotifer Symposium

Czech Academy of Sciences Publication Activity Database

Devetter, Miloslav; Fontaneto, D.; Jersabek, Ch.D.; Welch, D.B.M.; May, L.; Walsh, E.J.

2017-01-01

Roč. 796, č. 1 (2017), s. 1-6 ISSN 0018-8158 Institutional support: RVO:60077344 Keywords : evolving rotifers * 14th International Rotifer Symposium * evolving science Subject RIV: EG - Zoology OBOR OECD: Zoology Impact factor: 2.056, year: 2016

Dental Infection and Pregnancy: the Lack of Treatment by the Dental Professional Evolving to a Complex Maxillofacial Infection.

Science.gov (United States)

Pereira, Rodrigo Dos Santos; Gomes-Ferreira, Pedro Henrique Silva; Bonardi, João Paulo; Silva, Jonathan Ribeiro da; Latini, Gustavo Lima; Hochuli-Vieira, Eduardo

2017-11-01

Infections of the maxillofacial complex caused by caries disease are common in dental practice. The professionals have to have technical knowledge to treat it at the onset of the condition and avoid the spread to deep anatomical spaces of face and neck, which can implicate in a risk of patients' life.In Brazil, current dental professionals usually denied oral surgical treatments in patients with some clinical conditions, not because of fear to resolve it but for lack of knowledge to treat it. An example of these conditionals is pregnancy. It is well known that during the pregnancy period, the patient can be treated in the correct period of gestation. Early diagnosis is crucial for effective therapy in serious infections. The treatment has to be crucial during pregnancy because of the potentially fatal situation that the disease can create to the pregnant woman and the fetus.The aim of this article is to demonstrate a case of dental caries in a pregnant patient, which was evaluated by other professionals and had the treatment denied, evolving to a serious maxillofacial infection.

E2F5 status significantly improves malignancy diagnosis of epithelial ovarian cancer

KAUST Repository

Kothandaraman, Narasimhan

2010-02-24

Background: Ovarian epithelial cancer (OEC) usually presents in the later stages of the disease. Factors, especially those associated with cell-cycle genes, affecting the genesis and tumour progression for ovarian cancer are largely unknown. We hypothesized that over-expressed transcription factors (TFs), as well as those that are driving the expression of the OEC over-expressed genes, could be the key for OEC genesis and potentially useful tissue and serum markers for malignancy associated with OEC.Methods: Using a combination of computational (selection of candidate TF markers and malignancy prediction) and experimental approaches (tissue microarray and western blotting on patient samples) we identified and evaluated E2F5 transcription factor involved in cell proliferation, as a promising candidate regulatory target in early stage disease. Our hypothesis was supported by our tissue array experiments that showed E2F5 expression only in OEC samples but not in normal and benign tissues, and by significantly positively biased expression in serum samples done using western blotting studies.Results: Analysis of clinical cases shows that of the E2F5 status is characteristic for a different population group than one covered by CA125, a conventional OEC biomarker. E2F5 used in different combinations with CA125 for distinguishing malignant cyst from benign cyst shows that the presence of CA125 or E2F5 increases sensitivity of OEC detection to 97.9% (an increase from 87.5% if only CA125 is used) and, more importantly, the presence of both CA125 and E2F5 increases specificity of OEC to 72.5% (an increase from 55% if only CA125 is used). This significantly improved accuracy suggests possibility of an improved diagnostics of OEC. Furthermore, detection of malignancy status in 86 cases (38 benign, 48 early and late OEC) shows that the use of E2F5 status in combination with other clinical characteristics allows for an improved detection of malignant cases with sensitivity

Oxygen microclusters in Czochralski-grown Si probed by positron annihilation

International Nuclear Information System (INIS)

Uedono, Akira; Wei Long; Tanigawa, Shoichiro; Kawano, Takao; Ikari, Atsushi; Kawakami, Kazuto; Itoh, Hisayoshi.

1994-01-01

Trapping of positrons by oxygen microclusters in Czochralski-grown Si was studied. Lifetime spectra of positrons were measured for Si specimens annealed in the temperature range between 450degC and 1000degC. Positrons were found to be trapped by oxygen microclusters, and the trapping rate of positrons into such defects increased with increasing annealing temperature. In order to investigate the clustering behaviors of oxygen atoms in more derail, vacancy-oxygen complexes, V n O m (n,m=1,2, ···), were introduced by 3MeV electron irradiation. The concentration of monovacancy-oxygen complexes VO m (m=2,3, ···) increased with increasing annealing temperature. These facts were attributed that the oxygen microclusters, O m , were introduced by annealing above 700degC. (author)

Investigating the subsurface connection beneath Cerro Negro volcano and the El Hoyo Complex, Nicaragua

Science.gov (United States)

Venugopal, Swetha; Moune, Séverine; Williams-Jones, Glyn

2016-10-01

Cerro Negro, the youngest volcano along the Central American Volcanic Belt (CAVB), is a polygenetic cinder cone with relatively frequent basaltic eruptions. The neighbouring El Hoyo complex, of which Las Pilas is the dominant edifice, is a much larger and older complex with milder and less frequent eruptions. Previous studies have suggested a deep link beneath these two closely spaced volcanoes (McKnight, 1995; MacQueen, 2013). Melt inclusions were collected from various tephra samples in order to determine whether a connection exists and to delineate the features of this link. Major, volatile, and trace elemental compositions reveal a distinct geochemical continuum with Cerro Negro defining the primitive endmember and El Hoyo representing the evolved endmember. Magmatic conditions at the time of melt inclusion entrapment were estimated with major and volatile contents: 2.4 kbar and 1170 °C for Cerro Negro melts and 1.3 kbar and 1130 °C for El Hoyo melts with an overall oxygen fugacity at the NNO buffer. Trace element contents are distinct and suggest Cerro Negro magmas fractionally crystallise while El Hoyo magmas are a mix between primitive Cerro Negro melts and residual and evolved El Hoyo magma. Modelling of end member compositions with alphaMELTS confirms the unique nature of El Hoyo magmas as resulting from incremental mixing between Cerro Negro and residual evolved magma at 4 km depth. Combining all available literature data, this study presents a model of the interconnected subsurface plumbing system. This model considers the modern day analogue of the Lemptégy cinder cones in Massif Central, France and incorporates structurally controlled dykes. The main implications of this study are the classification of Cerro Negro as the newest conduit within the El Hoyo Complex as well as the potential re-activation of the El Hoyo edifice.

Single-cell printing to form three-dimensional lines of olfactory ensheathing cells

International Nuclear Information System (INIS)

Othon, Christina M; Ringeisen, Bradley R; Wu Xingjia; Anders, Juanita J

2008-01-01

Biological laser printing (BioLP(TM)) is a unique tool capable of printing high resolution two- and three-dimensional patterns of living mammalian cells, with greater than 95% viability. These results have been extended to primary cultured olfactory ensheathing cells (OECs), harvested from adult Sprague-Dawley rats. OECs have been found to provide stimulating environments for neurite outgrowth in spinal cord injury models. BioLP is unique in that small load volumes (∼μLs) are required to achieve printing, enabling low numbers of OECs to be harvested, concentrated and printed. BioLP was used to form several 8 mm lines of OECs throughout a multilayer hydrogel scaffold. The line width was as low as 20 μm, with most lines comprising aligned single cells. Fluorescent confocal microscopy was used to determine the functionality of the printed OECs, to monitor interactions between printed OECs, and to determine the extent of cell migration throughout the 3D scaffold. High-resolution printing of low cell count, harvested OECs is an important advancement for in vitro study of cell interactions and functionality. In addition, these cell-printed scaffolds may provide an alternative for spinal cord repair studies, as the single-cell patterns formed here are on relevant size scales for neurite outgrowth

CNPase Expression in Olfactory Ensheathing Cells

Directory of Open Access Journals (Sweden)

Christine Radtke

2011-01-01

Full Text Available A large body of work supports the proposal that transplantation of olfactory ensheathing cells (OECs into nerve or spinal cord injuries can promote axonal regeneration and remyelination. Yet, some investigators have questioned whether the transplanted OECs associate with axons and form peripheral myelin, or if they recruit endogenous Schwann cells that form myelin. Olfactory bulbs from transgenic mice expressing the enhanced green fluorescent protein (eGFP under the control of the 2-3-cyclic nucleotide 3-phosphodiesterase (CNPase promoter were studied. CNPase is expressed in myelin-forming cells throughout their lineage. We examined CNPase expression in both in situ in the olfactory bulb and in vitro to determine if OECs express CNPase commensurate with their myelination potential. eGFP was observed in the outer nerve layer of the olfactory bulb. Dissociated OECs maintained in culture had both intense eGFP expression and CNPase immunostaining. Transplantation of OECs into transected peripheral nerve longitudinally associated with the regenerated axons. These data indicate that OECs in the outer nerve layer of the olfactory bulb of CNPase transgenic mice express CNPase. Thus, while OECs do not normally form myelin on olfactory nerve axons, their expression of CNPase is commensurate with their potential to form myelin when transplanted into injured peripheral nerve.

Programming adaptive control to evolve increased metabolite production.

Science.gov (United States)

Chou, Howard H; Keasling, Jay D

2013-01-01

The complexity inherent in biological systems challenges efforts to rationally engineer novel phenotypes, especially those not amenable to high-throughput screens and selections. In nature, increased mutation rates generate diversity in a population that can lead to the evolution of new phenotypes. Here we construct an adaptive control system that increases the mutation rate in order to generate diversity in the population, and decreases the mutation rate as the concentration of a target metabolite increases. This system is called feedback-regulated evolution of phenotype (FREP), and is implemented with a sensor to gauge the concentration of a metabolite and an actuator to alter the mutation rate. To evolve certain novel traits that have no known natural sensors, we develop a framework to assemble synthetic transcription factors using metabolic enzymes and construct four different sensors that recognize isopentenyl diphosphate in bacteria and yeast. We verify FREP by evolving increased tyrosine and isoprenoid production.

Quantifying selection in evolving populations using time-resolved genetic data

Science.gov (United States)

Illingworth, Christopher J. R.; Mustonen, Ville

2013-01-01

Methods which uncover the molecular basis of the adaptive evolution of a population address some important biological questions. For example, the problem of identifying genetic variants which underlie drug resistance, a question of importance for the treatment of pathogens, and of cancer, can be understood as a matter of inferring selection. One difficulty in the inference of variants under positive selection is the potential complexity of the underlying evolutionary dynamics, which may involve an interplay between several contributing processes, including mutation, recombination and genetic drift. A source of progress may be found in modern sequencing technologies, which confer an increasing ability to gather information about evolving populations, granting a window into these complex processes. One particularly interesting development is the ability to follow evolution as it happens, by whole-genome sequencing of an evolving population at multiple time points. We here discuss how to use time-resolved sequence data to draw inferences about the evolutionary dynamics of a population under study. We begin by reviewing our earlier analysis of a yeast selection experiment, in which we used a deterministic evolutionary framework to identify alleles under selection for heat tolerance, and to quantify the selection acting upon them. Considering further the use of advanced intercross lines to measure selection, we here extend this framework to cover scenarios of simultaneous recombination and selection, and of two driver alleles with multiple linked neutral, or passenger, alleles, where the driver pair evolves under an epistatic fitness landscape. We conclude by discussing the limitations of the approach presented and outlining future challenges for such methodologies.

Energized Oxygen : Speiser Current Sheet Bifurcation

Science.gov (United States)

George, D. E.; Jahn, J. M.

2017-12-01

A single population of energized Oxygen (O+) is shown to produce a cross-tail bifurcated current sheet in 2.5D PIC simulations of the magnetotail without the influence of magnetic reconnection. Treatment of oxygen in simulations of space plasmas, specifically a magnetotail current sheet, has been limited to thermal energies despite observations of and mechanisms which explain energized ions. We performed simulations of a homogeneous oxygen background, that has been energized in a physically appropriate manner, to study the behavior of current sheets and magnetic reconnection, specifically their bifurcation. This work uses a 2.5D explicit Particle-In-a-Cell (PIC) code to investigate the dynamics of energized heavy ions as they stream Dawn-to-Dusk in the magnetotail current sheet. We present a simulation study dealing with the response of a current sheet system to energized oxygen ions. We establish a, well known and studied, 2-species GEM Challenge Harris current sheet as a starting point. This system is known to eventually evolve and produce magnetic reconnection upon thinning of the current sheet. We added a uniform distribution of thermal O+ to the background. This 3-species system is also known to eventually evolve and produce magnetic reconnection. We add one additional variable to the system by providing an initial duskward velocity to energize the O+. We also traced individual particle motion within the PIC simulation. Three main results are shown. First, energized dawn- dusk streaming ions are clearly seen to exhibit sustained Speiser motion. Second, a single population of heavy ions clearly produces a stable bifurcated current sheet. Third, magnetic reconnection is not required to produce the bifurcated current sheet. Finally a bifurcated current sheet is compatible with the Harris current sheet model. This work is the first step in a series of investigations aimed at studying the effects of energized heavy ions on magnetic reconnection. This work differs

Oxygen microclusters in Czochralski-grown Si probed by positron annihilation

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Wei Long; Tanigawa, Shoichiro [Tsukuba Univ., Ibaraki (Japan). Inst. of Materials Science; Kawano, Takao; Ikari, Atsushi; Kawakami, Kazuto; Itoh, Hisayoshi

1994-08-01

Trapping of positrons by oxygen microclusters in Czochralski-grown Si was studied. Lifetime spectra of positrons were measured for Si specimens annealed in the temperature range between 450degC and 1000degC. Positrons were found to be trapped by oxygen microclusters, and the trapping rate of positrons into such defects increased with increasing annealing temperature. In order to investigate the clustering behaviors of oxygen atoms in more derail, vacancy-oxygen complexes, V{sub n}O{sub m} (n,m=1,2, {center_dot}{center_dot}{center_dot}), were introduced by 3MeV electron irradiation. The concentration of monovacancy-oxygen complexes VO{sub m}(m=2,3, {center_dot}{center_dot}{center_dot}) increased with increasing annealing temperature. These facts were attributed that the oxygen microclusters, O{sub m}, were introduced by annealing above 700degC. (author).

The Role of Oxygen in the Evolution of Molybdenum Nitrogenase

Science.gov (United States)

Peters, J.; Boyd, E. S.; Hamilton, T. L.

2012-12-01

Since early in Earth's history, the supply of nitrogen (N) into the biosphere has been controlled by the activity of nitrogenase, an oxygen sensitive enzyme that catalyzes the reduction of dinitrogen gas (N2) to bioavailable ammonia. The most common form of nitrogenase harbors a complex molybdenum (Mo) cofactor at its active site [Mo-nitrogenase (Nif)], although other phylogenetically related (alternative) forms of nitrogenase that differ in their active-site metal composition also likely contribute NH3 in environments that are limiting in Mo. The solubility of Mo is significantly influenced by redox and this fact has been used to argue that that the iron (Fe)-dependent nitrogenase (Anf) was predominant prior to ~ 2.5 Ga because oceans were depleted in Mo and rich in Fe. This hypothesis, however, is inconsistent with recent phylogenetic data which strongly suggest that Anf is derived from Nif. Here, we examine the evolutionary history of the Nif enzyme complex in reference to the physiological, biochemical, and morphological strategies for reducing damage by molecular oxygen. A total of 189 nif operons were characterized and quantitatively mapped on a NifHDK concatenated phylogenetic tree. An overlay of the primary mode of metabolism, as defined as either anaerobic (AN) or aerobic/facultative aerobic (AFA), on the NifHDK tree indicates that Nif originated in an anoxic environment and was first acquired in an AFA lineage within the actinobacteria. The complexity of nif operons increased during the evolutionary history of Nif, with a pronounced increase observed during the transition from AN to AFA modes of metabolism. This increase in operon complexity is accompanied by a number of gene loss (nifI1 and nifI2) and gene acquisition (nifW, nifT, nifZ, nifQ) events, with variation in the overall composition of nif operons attributable to adaptations that mediated the toxicity of O2. Collectively, these results underscore the role of O2 in shaping the evolutionary

Unique in vivo properties of olfactory ensheathing cells that may contribute to neural repair and protection following spinal cord injury

Science.gov (United States)

Kocsis, Jeffery D.; Lankford, Karen L.; Sasaki, Masanori; Radtke, Christine

2009-01-01

Olfactory ensheathing cells (OECs) are specialized glial cells that guide olfactory receptor axons from the nasal mucosa into the brain where they make synaptic contacts in the olfactory bulb. While a number of studies have demonstrated that in vivo transplantation of OECs into injured spinal cord results in improved functional outcome, precise cellular mechanisms underlying this improvement are not fully understood. Current thinking is that OECs can encourage axonal regeneration, provide trophic support for injured neurons and for angiogenesis, and remyelinate axons. However, Schwann cell (SC) transplantation also results in significant functional improvement in animal models of spinal cord injury. In culture SCs and OECs share a number of phenotypic properties such as expression of the low affinity NGF receptor (p75). An important area of research has been to distinguish potential differences in the in vivo behavior of OECs and SCs to determine if one cell type may offer greater advantage as a cellular therapeutic candidate. In this review we focus on several unique features of OECs when they are transplanted into the spinal cord. PMID:19429149

Temperature and oxygenation during organ preservation: friends or foes?

Science.gov (United States)

Gilbo, Nicholas; Monbaliu, Diethard

2017-06-01

The liberalization of donor selection criteria in organ transplantation, with the increased use of suboptimal grafts, has stimulated interest in ischemia-reperfusion injury prevention and graft reconditioning. Organ preservation technologies are changing considerably, mostly through the reintroduction of dynamic machine preservation. Here, we review the current evidence on the role of temperature and oxygenation during dynamic machine preservation. A large but complex body of evidence exists and comparative studies are few. Oxygenation seems to support an advantageous effect in hypothermic machine preservation and is mandatory in normothermic machine preservation, although in the latter, supraphysiological oxygen tensions should be avoided. High-risk grafts, such as suboptimal organs, may optimally benefit from oxygenated perfusion conditions that support metabolism and activate mechanisms of repair such as subnormothermic machine preservation, controlled oxygenated rewarming, and normothermic machine preservation. For lower risk grafts, oxygenation during hypothermic machine preservation may sufficiently reduce injuries and recharge the cellular energy to secure functional recovery after transplantation. The relationship between temperature and oxygenation in organ preservation is more complex than physiological laws would suggest. Rather than one default perfusion temperature/oxygenation standard, perfusion protocols should be tailored for specific needs of grafts of different quality.

Effects of massive transfusion on oxygen availability

Directory of Open Access Journals (Sweden)

José Otávio Costa Auler Jr

Full Text Available OBJECTIVE: To determine oxygen derived parameters, hemodynamic and biochemical laboratory data (2,3 Diphosphoglycerate, lactate and blood gases analysis in patients after cardiac surgery who received massive blood replacement. DESIGN: Prospective study. SETTING: Heart Institute (Instituto do Coração, Hospital das Clínicas, Faculdade de Medicina, Universidade de São Paulo, Brazil. PARTICIPANTS: Twelve patients after cardiac surgery who received massive transfusion replacement; six of them evolved to a fatal outcome within the three-day postoperative follow-up. MEASUREMENTS AND MAIN RESULTS: The non-survivors group (n=6 presented high lactate levels and low P50 levels, when compared to the survivors group (p<0.05. Both groups presented an increase in oxygen consumption and O2 extraction, and there were no significant differences between them regarding these parameters. The 2,3 DPG levels were slightly reduced in both groups. CONCLUSIONS: This study shows that patients who are massively transfused following cardiovascular surgery present cell oxygenation disturbances probably as a result of O2 transport inadequacy.

How Life and Rocks Have Co-Evolved

Science.gov (United States)

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.

An evolving network model with community structure

International Nuclear Information System (INIS)

Li Chunguang; Maini, Philip K

2005-01-01

Many social and biological networks consist of communities-groups of nodes within which connections are dense, but between which connections are sparser. Recently, there has been considerable interest in designing algorithms for detecting community structures in real-world complex networks. In this paper, we propose an evolving network model which exhibits community structure. The network model is based on the inner-community preferential attachment and inter-community preferential attachment mechanisms. The degree distributions of this network model are analysed based on a mean-field method. Theoretical results and numerical simulations indicate that this network model has community structure and scale-free properties

Surface oxygen vacancy and oxygen permeation flux limits of perovskite ion transport membranes

KAUST Repository

Hunt, Anton; Dimitrakopoulos, Georgios; Ghoniem, Ahmed F.

2015-01-01

© 2015 Elsevier B.V. The mechanisms and quantitative models for how oxygen is separated from air using ion transport membranes (ITMs) are not well understood, largely due to the experimental complexity for determining surface exchange reactions

Highly sensitive time resolved singlet oxygen luminescence detection using LEDs as the excitation source

International Nuclear Information System (INIS)

Hackbarth, S; Schlothauer, J; Preuss, A; Röder, B

2013-01-01

For the first time singlet oxygen luminescence kinetics in living cells were detected at high precision using LED light for excitation. As LED technology evolves, the light intensity emitted by standard LEDs allows photosensitized singlet oxygen luminescence detection in solution and cell suspensions. We present measurements superior to those of most actual laser powered setups regarding precision of singlet oxygen kinetics in solutions and cell suspensions. Data presented here show that LED based setups allow the determination of the photosensitizer triplet and singlet oxygen decay times in vitro with an accuracy of 0.1 μs. This enables monitoring of the photosensitizer efficiency and interaction with the cellular components using illumination doses small enough not to cause cell death. (letter)

Synthesis and characterization of new bifunctional nanocomposites possessing upconversion and oxygen-sensing properties

International Nuclear Information System (INIS)

Liu Lina; Li Bin; Qin Ruifei; Zhao Haifeng; Ren Xinguang; Su Zhongmin

2010-01-01

A new type of bifunctional nanocomposites for biomedical applications, upconversion NaY F 4 :Y b 3+ , Tm 3+ nanoparticles coated with Ru(II) complex chemically doped SiO 2 , has been developed by combining the useful functions of upconversion and oxygen-sensing properties into one nanoparticle. NaY F 4 :Y b 3+ , Tm 3+ nanoparticles were successfully coated with an Ru(II) complex doped SiO 2 shell with a thickness of ∼ 30 nm, and the surface of the SiO 2 was functionalized with amines. The obtained nanocomposites exhibited bright blue upconversion emission, and the luminescent emission intensity of the Ru(II) complex in the nanocomposites was sensitive to oxygen. Compared with the simple mixture of Ru(II) complex and SiO 2 , the core-shell nanocomposites showed better linearity between emission intensity of Ru(II) complex and oxygen concentrations. These bifunctional nanocomposites may find applications in biochemical and biomedical fields, such as biolabels and optical oxygen sensors, which can measure the oxygen concentrations in biological fluids.

Autopoietic Automata: Complexity Issues in Offspring-Producing Evolving Processes

Czech Academy of Sciences Publication Activity Database

Wiedermann, Jiří

2007-01-01

Roč. 383, č. 2-3 (2007), s. 260-269 ISSN 0304-3975 R&D Projects: GA AV ČR 1ET100300517 Institutional research plan: CEZ:AV0Z10300504 Keywords : autopoietic automata * self-reproducing automata * interactive Turing machine * simulation * computational complexity Subject RIV: IN - Informatics, Computer Science Impact factor: 0.735, year: 2007

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

Science.gov (United States)

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.

Myelination and nodal formation of regenerated peripheral nerve fibers following transplantation of acutely prepared olfactory ensheathing cells

Science.gov (United States)

Dombrowski, Mary A.; Sasaki, Masanori; Lankford, Karen L.; Kocsis, Jeffery D.; Radtke, Christine

2009-01-01

Transplantation of olfactory ensheathing cells (OECs) into injured spinal cord results in improved functional outcome. Mechanisms suggested to account for this functional improvement include axonal regeneration, remyelination and neuroprotection. OECs transplanted into transected peripheral nerve have been shown to modify peripheral axonal regeneration and functional outcome. However, little is known of the detailed integration of OECs at the transplantation site in peripheral nerve. To address this issue cells populations enriched in OECs were isolated from the olfactory bulbs of adult green fluorescent protein (GFP)-expressing transgenic rats and transplanted into a sciatic nerve crush lesion which transects all axons. Five weeks to six months after transplantation the nerves were studied histologically. GFP-expressing OECs survived in the lesion and distributed longitudinally across the lesion zone. The internodal regions of individual teased fibers distal to the transection site were characterized by GFP expression in the cytoplasmic and nuclear compartments of cells surrounding the axons. Immuno-electron microscopy for GFP indicated that the transplanted OECs formed peripheral type myelin. Immunostaining for sodium channel and Caspr revealed a high density of Nav1.6 at the newly formed nodes of Ranvier which were flanked by paranodal Caspr staining. These results indicate that transplanted OECs extensively integrate into transected peripheral nerve and form myelin on regenerated peripheral nerve fibers, and that nodes of Ranvier of these axons display proper sodium channel organization. PMID:17112480

Micro-oxygenation does not eliminate hydrogen sulfide and mercaptans from wine; it simply shifts redox and complex-related equilibria to reversible oxidized species and complexed forms.

Science.gov (United States)

Vela, Eduardo; Hernandez-Orte, Purificación; Franco-Luesma, Ernesto; Ferreira, Vicente

2018-03-15

This work seeks to assess the effects of micro-oxygenation (MOX) on the present and potential levels of Volatile Sulfur Compounds (VSCs) of wine. With such purpose, three red wines with a tendency to develop sulfury off-odors were subjected to three different MOX conditions (4.4-20mg/L delivered at 0.05 or 0.2mg/L/day). Samples were further subjected to Accelerated Reductive aging (AR) and analyzed for free and Brine Releasable (BR) VSCs and redox potential. Although MOX induced strong decreases in the levels of all free VSCs, hardly affected the ability of the wine to release back hydrogen sulfide and other mercaptans during AR-aging. During aging BR-levels of MOX samples became in most cases similar or higher than non-oxygenated controls. BR-levels and the fractions free/BR follow characteristic sigmoid plots when represented versus redox potential suggesting that all changes are the result of reversible equilibria between free, metal-complexed and oxidized forms of VSCs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnetic field effects on spectrally resolved lifetime of on-line oxygen monitoring using magneto-optic probes

Science.gov (United States)

Mermut, O.; Gallant, P.; Le Bouch, N.; Leclair, S.; Noiseux, I.; Vernon, M.; Morin, J.-F.; Diamond, K.; Patterson, M. S.; Samkoe, K.; Pogue, B.

2009-02-01

Multimodal agents that serve as both probes for contrast and light-activated effectors of cellular processes in diseased tissue were developed. These agents were introduced into multicellular tumor spheroids (3D tissue models) and in the chorioallantoic membrane (CAM) of a chicken embryo. The luminescence decay was examined using a novel technique involving a spectrally-resolved fluorescence lifetime apparatus integrated with a weak electromagnet. A spectrallyresolved lifetime setup was used to identify magneto-optic species sensitive to magnetic field effects and distinguish from background emissions. We demonstrate that the applied magnetic fields can alter reaction rates and product distribution of some dyes detected by time- and spectrally-resolved luminescence changes. We will discuss the use of exogenous magneto-optical probes taken up in tumors to both induce phototoxicity, a process that is governed by complex and dynamically evolving mechanisms involving reactive oxygen species, and monitor treatment progress. The magnetic field enhancement, measured over a range of weak fields (0-300 mT) is correlated to oxygenation and may be used to monitor dynamic changes occurring due to oxygen consumption over the course of photodynamic therapy. Such online measurements provide the possibility to derive real-time information about response to treatment via monitoring magnetic field enhancement/suppression of the time-resolved, spectrally-resolved luminescence of the probe at the site of the treatment directly. Magnetic perturbation of lifetime can serve as a status reporter, providing optical feedback of oxygen-mediated treatments in situ and allowing for real-time adjustment of a phototherapy treatment plan.

Redox signaling in acute oxygen sensing

Directory of Open Access Journals (Sweden)

Lin Gao

2017-08-01

Full Text Available Acute oxygen (O2 sensing is essential for individuals to survive under hypoxic conditions. The carotid body (CB is the main peripheral chemoreceptor, which contains excitable and O2-sensitive glomus cells with O2-regulated ion channels. Upon exposure to acute hypoxia, inhibition of K+ channels is the signal that triggers cell depolarization, transmitter release and activation of sensory fibers that stimulate the brainstem respiratory center to produce hyperventilation. The molecular mechanisms underlying O2 sensing by glomus cells have, however, remained elusive. Here we discuss recent data demonstrating that ablation of mitochondrial Ndufs2 gene selectively abolishes sensitivity of glomus cells to hypoxia, maintaining responsiveness to hypercapnia or hypoglycemia. These data suggest that reactive oxygen species and NADH generated in mitochondrial complex I during hypoxia are signaling molecules that modulate membrane K+ channels. We propose that the structural substrates for acute O2 sensing in CB glomus cells are “O2-sensing microdomains” formed by mitochondria and neighboring K+ channels in the plasma membrane. Keywords: Hypoxia, Acute oxygen sensing, Peripheral chemoreceptors, Carotid body, Adrenal medulla, Mitochondrial complex I, Reactive oxygen species (ROS, Pyridine nucleotides

Evolving Neural Turing Machines for Reward-based Learning

DEFF Research Database (Denmark)

Greve, Rasmus Boll; Jacobsen, Emil Juul; Risi, Sebastian

2016-01-01

An unsolved problem in neuroevolution (NE) is to evolve artificial neural networks (ANN) that can store and use information to change their behavior online. While plastic neural networks have shown promise in this context, they have difficulties retaining information over longer periods of time...... version of the double T-Maze, a complex reinforcement-like learning problem. In the T-Maze learning task the agent uses the memory bank to display adaptive behavior that normally requires a plastic ANN, thereby suggesting a complementary and effective mechanism for adaptive behavior in NE....

Effects of motexafin gadolinium on tumor oxygenation and cellular oxygen consumption

International Nuclear Information System (INIS)

Donnelly, E.T.; Liu, Y.; Rockwell, S.; Magda, D.

2003-01-01

Full text: Recent work in our laboratory showed that motexafin gadolinium (MGd, Xcytrin), a drug currently in Phase III clinical trials as an adjuvant to radiation therapy, modulates the oxygen tensions in EMT6 tumors. The median pO 2 increased from the control value of 1.5±0.4 mmHg to 7.4 ± 3.8 mmHg six hours after treatment with 40 μmol/kg MGd and the percentage of severely hypoxic readings in the tumors ( 7 plateau phase EMT6 cells in 3 mL Dulbecco's Modified Eagle's Medium supplemented with 10% dialyzed fetal bovine serum, which contains no ascorbic acid. In the absence of ascorbic acid, 100 μM MGd did not alter the cellular oxygen consumption rate for EMT6 cells significantly. Marked inhibition of cellular oxygen consumption was observed when cells were incubated with 100 μM MGd in medium supplemented with equimolar ascorbic acid (a 31.5% decrease in consumption was observed after 6 hours of treatment). The 5% mannitol vehicle solution with equimolar ascorbic acid had no discernible effect on cellular oxygen consumption. Ascorbic acid may facilitate cellular uptake of MGd via the intermediate formation of a MGd-oxalate complex. These studies suggest that changes in cellular oxygen consumption could contribute to the changes in tumor oxygenation seen after administration of MGd. These experiments were supported by Pharmacyclics and training grant T32CA09085 from the NIH (E.T.D.). We thank Dr. Raymond Russell for allowing us to use his oxygen electrode apparatus

Effects of oxygen partial pressure on Li-air battery performance

Science.gov (United States)

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.

Natural selection promotes antigenic evolvability.

Science.gov (United States)

Graves, Christopher J; Ros, Vera I D; Stevenson, Brian; Sniegowski, Paul D; Brisson, Dustin

2013-01-01

The hypothesis that evolvability - the capacity to evolve by natural selection - is itself the object of natural selection is highly intriguing but remains controversial due in large part to a paucity of direct experimental evidence. The antigenic variation mechanisms of microbial pathogens provide an experimentally tractable system to test whether natural selection has favored mechanisms that increase evolvability. Many antigenic variation systems consist of paralogous unexpressed 'cassettes' that recombine into an expression site to rapidly alter the expressed protein. Importantly, the magnitude of antigenic change is a function of the genetic diversity among the unexpressed cassettes. Thus, evidence that selection favors among-cassette diversity is direct evidence that natural selection promotes antigenic evolvability. We used the Lyme disease bacterium, Borrelia burgdorferi, as a model to test the prediction that natural selection favors amino acid diversity among unexpressed vls cassettes and thereby promotes evolvability in a primary surface antigen, VlsE. The hypothesis that diversity among vls cassettes is favored by natural selection was supported in each B. burgdorferi strain analyzed using both classical (dN/dS ratios) and Bayesian population genetic analyses of genetic sequence data. This hypothesis was also supported by the conservation of highly mutable tandem-repeat structures across B. burgdorferi strains despite a near complete absence of sequence conservation. Diversification among vls cassettes due to natural selection and mutable repeat structures promotes long-term antigenic evolvability of VlsE. These findings provide a direct demonstration that molecular mechanisms that enhance evolvability of surface antigens are an evolutionary adaptation. The molecular evolutionary processes identified here can serve as a model for the evolution of antigenic evolvability in many pathogens which utilize similar strategies to establish chronic infections.

Natural selection promotes antigenic evolvability.

Directory of Open Access Journals (Sweden)

Christopher J Graves

Full Text Available The hypothesis that evolvability - the capacity to evolve by natural selection - is itself the object of natural selection is highly intriguing but remains controversial due in large part to a paucity of direct experimental evidence. The antigenic variation mechanisms of microbial pathogens provide an experimentally tractable system to test whether natural selection has favored mechanisms that increase evolvability. Many antigenic variation systems consist of paralogous unexpressed 'cassettes' that recombine into an expression site to rapidly alter the expressed protein. Importantly, the magnitude of antigenic change is a function of the genetic diversity among the unexpressed cassettes. Thus, evidence that selection favors among-cassette diversity is direct evidence that natural selection promotes antigenic evolvability. We used the Lyme disease bacterium, Borrelia burgdorferi, as a model to test the prediction that natural selection favors amino acid diversity among unexpressed vls cassettes and thereby promotes evolvability in a primary surface antigen, VlsE. The hypothesis that diversity among vls cassettes is favored by natural selection was supported in each B. burgdorferi strain analyzed using both classical (dN/dS ratios and Bayesian population genetic analyses of genetic sequence data. This hypothesis was also supported by the conservation of highly mutable tandem-repeat structures across B. burgdorferi strains despite a near complete absence of sequence conservation. Diversification among vls cassettes due to natural selection and mutable repeat structures promotes long-term antigenic evolvability of VlsE. These findings provide a direct demonstration that molecular mechanisms that enhance evolvability of surface antigens are an evolutionary adaptation. The molecular evolutionary processes identified here can serve as a model for the evolution of antigenic evolvability in many pathogens which utilize similar strategies to establish

Evolving a Method to Capture Science Stakeholder Inputs to Optimize Instrument, Payload, and Program Design

Science.gov (United States)

Clark, P. E.; Rilee, M. L.; Curtis, S. A.; Bailin, S.

2012-03-01

We are developing Frontier, a highly adaptable, stably reconfigurable, web-accessible intelligent decision engine capable of optimizing design as well as the simulating operation of complex systems in response to evolving needs and environment.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, I

Science.gov (United States)

2004-01-01

The Special Session: Oxygen in the Solar System, I, included the following reports:Oxygen in the Solar System: Origins of Isotopic and Redox Complexity; The Origin of Oxygen Isotope Variations in the Early Solar System; Solar and Solar-Wind Oxygen Isotopes and the Genesis Mission; Solar 18O/17O and the Setting for Solar Birth; Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites; Insight into Primordial Solar System Oxygen Reservoirs from Returned Cometary Samples; Tracing Meteorites to Their Sources Through Asteroid Spectroscopy; Redox Conditions Among the Terrestrial Planets; Redox Complexity in Martian Meteorites: Implications for Oxygen in the Terrestrial Planets; Implications of Sulfur Isotopes for the Evolution of Atmospheric Oxygen; Oxygen in the Outer Solar System; and On the Oxidation States of the Galilean Satellites: Implications for Internal Structures.

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

Science.gov (United States)

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.

A model for the emergence of cooperation, interdependence, and structure in evolving networks

Science.gov (United States)

Jain, Sanjay; Krishna, Sandeep

2001-01-01

Evolution produces complex and structured networks of interacting components in chemical, biological, and social systems. We describe a simple mathematical model for the evolution of an idealized chemical system to study how a network of cooperative molecular species arises and evolves to become more complex and structured. The network is modeled by a directed weighted graph whose positive and negative links represent "catalytic" and "inhibitory" interactions among the molecular species, and which evolves as the least populated species (typically those that go extinct) are replaced by new ones. A small autocatalytic set, appearing by chance, provides the seed for the spontaneous growth of connectivity and cooperation in the graph. A highly structured chemical organization arises inevitably as the autocatalytic set enlarges and percolates through the network in a short analytically determined timescale. This self organization does not require the presence of self-replicating species. The network also exhibits catastrophes over long timescales triggered by the chance elimination of "keystone" species, followed by recoveries.

Evolving cell models for systems and synthetic biology.

Science.gov (United States)

Cao, Hongqing; Romero-Campero, Francisco J; Heeb, Stephan; Cámara, Miguel; Krasnogor, Natalio

2010-03-01

This paper proposes a new methodology for the automated design of cell models for systems and synthetic biology. Our modelling framework is based on P systems, a discrete, stochastic and modular formal modelling language. The automated design of biological models comprising the optimization of the model structure and its stochastic kinetic constants is performed using an evolutionary algorithm. The evolutionary algorithm evolves model structures by combining different modules taken from a predefined module library and then it fine-tunes the associated stochastic kinetic constants. We investigate four alternative objective functions for the fitness calculation within the evolutionary algorithm: (1) equally weighted sum method, (2) normalization method, (3) randomly weighted sum method, and (4) equally weighted product method. The effectiveness of the methodology is tested on four case studies of increasing complexity including negative and positive autoregulation as well as two gene networks implementing a pulse generator and a bandwidth detector. We provide a systematic analysis of the evolutionary algorithm's results as well as of the resulting evolved cell models.

Design of the tool for periodic not evolvent profiles

Directory of Open Access Journals (Sweden)

Anisimov Roman

2017-01-01

Full Text Available The new approach to profiling of the tool for processing of parts with periodic not evolvent profiles are considered in the article The discriminatory analysis of periodic profiles including repetition of profile both in the plane of perpendicular axis of part, and in the plane of passing along part of axis is offered. In the basis of the offered profiling method the idea of space shaping by rated surface of product of tool surface lies. The big advantage of the offered approach in profiling is its combination with the analysis of parameters of process of engineering work. It allows to predict the accuracy and surface quality of product with not evolvent periodic profile. While using the offered approach the pinion cutter for processing of wheels with internal triangular teeths and mill for processing of the screw of the counter of consumption of liquid, complex profile of which consists of several formings, have been received

Oxygen measurements in thin ribbon silicon

Energy Technology Data Exchange (ETDEWEB)

Hyland, S L; Ast, D G; Baghdadi, A

1987-03-01

The oxygen content of thin silicon ribbons grown by the dendritic web technique was measured using a modification of the ASTM method based on Fourier transform infrared spectroscopy. Web silicon was found to have a high oxygen content, ranging from 13 to 19 ppma, calculated from the absorption peak associated with interstitial oxygen and using the new ASTM conversion coefficient. The oxygen concentration changed by about 10% along the growth direction of the ribbon. In some samples, a shoulder was detected on the absorption peak. A similar shoulder in Czochralski grown material has been variously interpreted in the literature as due to a complex of silicon, oxygen, and vacancies, or to a phase of SiO/sub 2/ developed along dislocations in the material. In the case of web silicon, it is not clear which is the correct interpretation.

Manipulating oxygen sublattice in ultrathin cuprates: a new direction to engineer oxides

NARCIS (Netherlands)

Samal, D.; Koster, Gertjan

2015-01-01

Atomic engineering of complex oxide thin films is now reaching a new paradigm: the possibility to control the cation coordination by oxygen anions. Here, we show two examples of stabilization of novel structural phases by manipulating the oxygen sublattices in complex Cu-based oxide thin films grown

An evolving systems-based methodology for healthcare planning.

Science.gov (United States)

Warwick, Jon; Bell, Gary

2007-01-01

Healthcare planning seems beset with problems at all hierarchical levels. These are caused by the 'soft' nature of many of the issues present in healthcare planning and the high levels of complexity inherent in healthcare services. There has, in recent years, been a move to utilize systems thinking ideas in an effort to gain a better understanding of the forces at work within the healthcare environment and these have had some success. This paper argues that systems-based methodologies can be further enhanced by metrication and modeling which assist in exploring the changed emergent behavior of a system resulting from management intervention. The paper describes the Holon Framework as an evolving systems-based approach that has been used to help clients understand complex systems (in the education domain) that would have application in the analysis of healthcare problems.

Smart signal processing for an evolving electric grid

Science.gov (United States)

Silva, Leandro Rodrigues Manso; Duque, Calos Augusto; Ribeiro, Paulo F.

2015-12-01

Electric grids are interconnected complex systems consisting of generation, transmission, distribution, and active loads, recently called prosumers as they produce and consume electric energy. Additionally, these encompass a vast array of equipment such as machines, power transformers, capacitor banks, power electronic devices, motors, etc. that are continuously evolving in their demand characteristics. Given these conditions, signal processing is becoming an essential assessment tool to enable the engineer and researcher to understand, plan, design, and operate the complex and smart electronic grid of the future. This paper focuses on recent developments associated with signal processing applied to power system analysis in terms of characterization and diagnostics. The following techniques are reviewed and their characteristics and applications discussed: active power system monitoring, sparse representation of power system signal, real-time resampling, and time-frequency (i.e., wavelets) applied to power fluctuations.

Oxygen incorporation into GST phase-change memory matrix

Energy Technology Data Exchange (ETDEWEB)

Golovchak, R., E-mail: holovchakr@apsu.edu [Department of Physics and Astronomy, Austin Peay State University, Clarksville, TN 37044 (United States); Choi, Y.G. [Department of Materials Science and Engineering, Korea Aerospace University, Gyeonggi 412-791 (Korea, Republic of); Kozyukhin, S. [Kurnakov Institute of General and Inorganic Chemistry of RAS, 31 Leninsky Pr., Moscow 119991 (Russian Federation); National Research Tomsk State University, 36 Lenin Pr., Tomsk 634050 (Russian Federation); Chigirinsky, Yu. [Scientific-Research Physicotechnical Institute at the Nizhnii Novgorod State University, Nizhnii Novgorod 603600 (Russian Federation); Kovalskiy, A.; Xiong-Skiba, P.; Trimble, J. [Department of Physics and Astronomy, Austin Peay State University, Clarksville, TN 37044 (United States); Pafchek, R.; Jain, H. [Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States)

2015-03-30

Graphical abstract: - Highlights: • Surfaces of GST-225 films are depleted in Te as a result of the reaction with oxygen. • Top layers of oxidized GST-225 are formed by Sb and Ge oxide complexes. • Depth profiles of Sb and Ge oxide complexes are found to be different. • Crystallization at 300 °C in O{sub 2} atmosphere leads to Ge redistribution. - Abstract: Structural changes in amorphous and crystallized GST-225 films induced by the reaction with oxygen are studied at different depth scales. The mechanism of interaction of the very top surface layers with oxygen is studied with low-energy ion scattering (LEIS) technique, while the modifications of chemistry in the underlying surface layers are investigated with high-resolution X-ray photoelectron spectroscopy (XPS). The changes averaged through the overall film thickness are characterized by micro-Raman spectroscopy. The oxygen exposure leads to a depletion of GST-225 film surfaces in Te and formation of the antimony and germanium oxides. The antimony oxide complexes are found throughout the whole thickness of the films after their prolonged storage in air, whereas no evidence for formation of pure GeO{sub 2} phase is found in the volume of the films through Raman spectroscopy. A tendency to form Ge-rich phase within the ∼10 nm surface layer is additionally observed by LEIS profiling during crystallization of GST-225 film at 300 °C in oxygen atmosphere.

The Pathway for Oxygen: Tutorial Modelling on Oxygen Transport from Air to Mitochondrion: The Pathway for Oxygen.

Science.gov (United States)

Bassingthwaighte, James B; Raymond, Gary M; Dash, Ranjan K; Beard, Daniel A; Nolan, Margaret

2016-01-01

The 'Pathway for Oxygen' is captured in a set of models describing quantitative relationships between fluxes and driving forces for the flux of oxygen from the external air source to the mitochondrial sink at cytochrome oxidase. The intervening processes involve convection, membrane permeation, diffusion of free and heme-bound O2 and enzymatic reactions. While this system's basic elements are simple: ventilation, alveolar gas exchange with blood, circulation of the blood, perfusion of an organ, uptake by tissue, and consumption by chemical reaction, integration of these pieces quickly becomes complex. This complexity led us to construct a tutorial on the ideas and principles; these first PathwayO2 models are simple but quantitative and cover: (1) a 'one-alveolus lung' with airway resistance, lung volume compliance, (2) bidirectional transport of solute gasses like O2 and CO2, (3) gas exchange between alveolar air and lung capillary blood, (4) gas solubility in blood, and circulation of blood through the capillary syncytium and back to the lung, and (5) blood-tissue gas exchange in capillaries. These open-source models are at Physiome.org and provide background for the many respiratory models there.

Physiological complexity of acute traumatic brain injury in patients treated with a brain oxygen protocol: utility of symbolic regression in predictive modeling of a dynamical system.

Science.gov (United States)

Narotam, Pradeep K; Morrison, John F; Schmidt, Michael D; Nathoo, Narendra

2014-04-01

Predictive modeling of emergent behavior, inherent to complex physiological systems, requires the analysis of large complex clinical data streams currently being generated in the intensive care unit. Brain tissue oxygen protocols have yielded outcome benefits in traumatic brain injury (TBI), but the critical physiological thresholds for low brain oxygen have not been established for a dynamical patho-physiological system. High frequency, multi-modal clinical data sets from 29 patients with severe TBI who underwent multi-modality neuro-clinical care monitoring and treatment with a brain oxygen protocol were analyzed. The inter-relationship between acute physiological parameters was determined using symbolic regression (SR) as the computational framework. The mean patient age was 44.4±15 with a mean admission GCS of 6.6±3.9. Sixty-three percent sustained motor vehicle accidents and the most common pathology was intra-cerebral hemorrhage (50%). Hospital discharge mortality was 21%, poor outcome occurred in 24% of patients, and good outcome occurred in 56% of patients. Criticality for low brain oxygen was intracranial pressure (ICP) ≥22.8 mm Hg, for mortality at ICP≥37.1 mm Hg. The upper therapeutic threshold for cerebral perfusion pressure (CPP) was 75 mm Hg. Eubaric hyperoxia significantly impacted partial pressure of oxygen in brain tissue (PbtO2) at all ICP levels. Optimal brain temperature (Tbr) was 34-35°C, with an adverse effect when Tbr≥38°C. Survivors clustered at [Formula: see text] Hg vs. non-survivors [Formula: see text] 18 mm Hg. There were two mortality clusters for ICP: High ICP/low PbtO2 and low ICP/low PbtO2. Survivors maintained PbtO2 at all ranges of mean arterial pressure in contrast to non-survivors. The final SR equation for cerebral oxygenation is: [Formula: see text]. The SR-model of acute TBI advances new physiological thresholds or boundary conditions for acute TBI management: PbtO2≥25 mmHg; ICP≤22 mmHg; CPP≈60-75�

Complexity science and leadership in healthcare.

Science.gov (United States)

Burns, J P

2001-10-01

The emerging field of complexity science offers an alternative leadership strategy for the chaotic, complex healthcare environment. A survey revealed that healthcare leaders intuitively support principles of complexity science. Leadership that uses complexity principles offers opportunities in the chaotic healthcare environment to focus less on prediction and control and more on fostering relationships and creating conditions in which complex adaptive systems can evolve to produce creative outcomes.

Oxygen incorporation effects in annealed epitaxial La(1-x)SrxMnO3 thin films

International Nuclear Information System (INIS)

Petrisor, T.; Gabor, M. S.; Tiusan, C.; Boulle, A.; Bellouard, C.; Pana, O.; Petrisor, T.

2011-01-01

This paper presents our results regarding oxygen incorporation effects in epitaxial La (1-x) Sr x MnO 3 thin films, deposited on SrTiO 3 (001) single crystal substrates, by annealing in different gas mixtures of argon and oxygen. A particular emphasis is placed on the correlation of structural properties with the magnetic properties of the films, Curie temperature, and coercive field. In this sense, we demonstrate that the evolution of the diffuse part of the ω-scans performed on the films are due to oxygen excess in the film lattice, which creates cationic vacancies within the films. Also, we show that two regimes of oxygen incorporation in the films exist, one in which the films evolve toward a single phase and oxygen stoichiometry is recovered, and a second one dominated by oxygen over-doping effects. In order to support our study, XPS measurements were performed, from which we have evaluated the Mn 3+ /Mn 4+ ionic ratio.

A Weighted Evolving Network with Community Size Preferential Attachment

International Nuclear Information System (INIS)

Zhuo Zhiwei; Shan Erfang

2010-01-01

Community structure is an important characteristic in real complex network. It is a network consists of groups of nodes within which links are dense but among which links are sparse. In this paper, the evolving network include node, link and community growth and we apply the community size preferential attachment and strength preferential attachment to a growing weighted network model and utilize weight assigning mechanism from BBV model. The resulting network reflects the intrinsic community structure with generalized power-law distributions of nodes' degrees and strengths.

Ordered oxygen deficient '112' perovskites, LnBaCo2 : complex ...

Indian Academy of Sciences (India)

Administrator

are labeled on the graph. .... in agreement with Kanamori Goodenough rules. In sum- mary, these results ... exhibit very rich phase diagrams as illustrated in figure 9. The latter .... which make that the control of oxygen content in these phases is ...

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

Science.gov (United States)

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.

Organic evaporator steam valve failure

International Nuclear Information System (INIS)

Jacobs, R.A.

1992-01-01

Defense Waste Processing Facility (DWPF) Technical has requested an analysis of the capacity of the Organic Evaporator (OE) condenser (OEC) be performed to determine its capability in the case where the OE steam flow control valve fails open. Calculations of the OE boilup and the OEC heat transfer coefficient indicate the OEC will have more than enough capacity to remove the heat at maximum OE boilup. In fact, the Salt Cell Vent Condenser (SCVC) should also have sufficient capacity to handle the maximum OE boilup. Therefore, it would require simultaneous loss of OEC and/or SCVC condensing capacity for the steam valve failure to cause high benzene in the Process Vessel Vent System (PVVS)

The ISO Long Wavelength Spectrometer line spectrum of VY Canis Majoris and other oxygen-rich evolved stars

NARCIS (Netherlands)

Polehampton, E. T.; Menten, K. M.; van der Tak, F. F. S.; White, G. J.

Context. The far-infrared spectra of circumstellar envelopes around various oxygen-rich stars were observed using the ISO Long Wavelength Spectrometer (LWS). These have been shown to be spectrally rich, particularly in water lines, indicating a high H2O abundance. Aims. We have examined high

Conceptual development of ethical climate and its impacts on individuals and organizations

OpenAIRE

Aksoy, Seval; Erdil, Oya; Ertürk, Alper

2017-01-01

The concept of “Organizational Ethical Climate (OEC)” is a subject matter of organizational attitude research study on which many researchers have been conducted so far, especially after 2000’s. In this research, relationships among OEC and organizational identification (OI), commitment (OC) and personorganization fit (POF) are analyzed through an empirical research conducted in manufacturing firms located in Kocaeli. Results indicate that there are positive relationships between OEC and OI, ...

Evolvability Is an Evolved Ability: The Coding Concept as the Arch-Unit of Natural Selection.

Science.gov (United States)

Janković, Srdja; Ćirković, Milan M

2016-03-01

Physical processes that characterize living matter are qualitatively distinct in that they involve encoding and transfer of specific types of information. Such information plays an active part in the control of events that are ultimately linked to the capacity of the system to persist and multiply. This algorithmicity of life is a key prerequisite for its Darwinian evolution, driven by natural selection acting upon stochastically arising variations of the encoded information. The concept of evolvability attempts to define the total capacity of a system to evolve new encoded traits under appropriate conditions, i.e., the accessible section of total morphological space. Since this is dependent on previously evolved regulatory networks that govern information flow in the system, evolvability itself may be regarded as an evolved ability. The way information is physically written, read and modified in living cells (the "coding concept") has not changed substantially during the whole history of the Earth's biosphere. This biosphere, be it alone or one of many, is, accordingly, itself a product of natural selection, since the overall evolvability conferred by its coding concept (nucleic acids as information carriers with the "rulebook of meanings" provided by codons, as well as all the subsystems that regulate various conditional information-reading modes) certainly played a key role in enabling this biosphere to survive up to the present, through alterations of planetary conditions, including at least five catastrophic events linked to major mass extinctions. We submit that, whatever the actual prebiotic physical and chemical processes may have been on our home planet, or may, in principle, occur at some time and place in the Universe, a particular coding concept, with its respective potential to give rise to a biosphere, or class of biospheres, of a certain evolvability, may itself be regarded as a unit (indeed the arch-unit) of natural selection.

Toxic and nontoxic components of botulinum neurotoxin complex are evolved from a common ancestral zinc protein

International Nuclear Information System (INIS)

Inui, Ken; Sagane, Yoshimasa; Miyata, Keita; Miyashita, Shin-Ichiro; Suzuki, Tomonori; Shikamori, Yasuyuki; Ohyama, Tohru; Niwa, Koichi; Watanabe, Toshihiro

2012-01-01

Highlights: ► BoNT and NTNHA proteins share a similar protein architecture. ► NTNHA and BoNT were both identified as zinc-binding proteins. ► NTNHA does not have a classical HEXXH zinc-coordinating motif similar to that found in all serotypes of BoNT. ► Homology modeling implied probable key residues involved in zinc coordination. -- Abstract: Zinc atoms play an essential role in a number of enzymes. Botulinum neurotoxin (BoNT), the most potent toxin known in nature, is a zinc-dependent endopeptidase. Here we identify the nontoxic nonhemagglutinin (NTNHA), one of the BoNT-complex constituents, as a zinc-binding protein, along with BoNT. A protein structure classification database search indicated that BoNT and NTNHA share a similar domain architecture, comprising a zinc-dependent metalloproteinase-like, BoNT coiled-coil motif and concanavalin A-like domains. Inductively coupled plasma-mass spectrometry analysis demonstrated that every single NTNHA molecule contains a single zinc atom. This is the first demonstration of a zinc atom in this protein, as far as we know. However, the NTNHA molecule does not possess any known zinc-coordinating motif, whereas all BoNT serotypes possess the classical HEXXH motif. Homology modeling of the NTNHA structure implied that a consensus K-C-L-I-K-X 35 -D sequence common among all NTNHA serotype molecules appears to coordinate a single zinc atom. These findings lead us to propose that NTNHA and BoNT may have evolved distinct functional specializations following their branching out from a common ancestral zinc protein.

Evolving colon injury management: a review.

Science.gov (United States)

Greer, Lauren T; Gillern, Suzanne M; Vertrees, Amy E

2013-02-01

The colon is the second most commonly injured intra-abdominal organ in penetrating trauma. Management of traumatic colon injuries has evolved significantly over the past 200 years. Traumatic colon injuries can have a wide spectrum of severity, presentation, and management options. There is strong evidence that most non-destructive colon injuries can be successfully managed with primary repair or primary anastomosis. The management of destructive colon injuries remains controversial with most favoring resection with primary anastomosis and others favor colonic diversion in specific circumstances. The historical management of traumatic colon injuries, common mechanisms of injury, demographics, presentation, assessment, diagnosis, management, and complications of traumatic colon injuries both in civilian and military practice are reviewed. The damage control revolution has added another layer of complexity to management with continued controversy.

Natural selection promotes antigenic evolvability

NARCIS (Netherlands)

Graves, C.J.; Ros, V.I.D.; Stevenson, B.; Sniegowski, P.D.; Brisson, D.

2013-01-01

The hypothesis that evolvability - the capacity to evolve by natural selection - is itself the object of natural selection is highly intriguing but remains controversial due in large part to a paucity of direct experimental evidence. The antigenic variation mechanisms of microbial pathogens provide

Unusual Reactivity of the Martian Soil: Oxygen Release Upon Humidification

Science.gov (United States)

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.

MK classification of evolved blue stars in the halo

International Nuclear Information System (INIS)

Garrison, R.F.

1987-01-01

The problem of the masses and origin of the evolved blue stars is very complex. No single approach can give all the answers unambiguously; it would be naive to suppose otherwise. The MK process and the MK system give a perspective which complements photometric, kinematic, high dispersion and other quantitative data. It is useful to know which stars are similar (or not) in spectral morphology, so that interesting candidates can be selected for further study. In many cases, the gross physical characteristics can be fairly well determined by use of the MK System. 8 references

The Evolving Role of Physicians - Don’t Forget the Generalist Primary Care Providers; Comment on “Non-physician Clinicians in Sub-Saharan Africa and the Evolving Role of Physicians”

Directory of Open Access Journals (Sweden)

Vincent Kalumire Cubaka

2016-10-01

Full Text Available The editorial “Non-physician Clinicians in Sub-Saharan Africa and the Evolving Role of Physicians” by Eyal et al describes non-physician clinicians’ (NPC need for mentorship and support from physicians. We emphasise the same need of support for front line generalist primary healthcare providers who carry out complex tasks yet may have an inadequate skill mix.

Effect of oxygen on the complexing and electrochemical processes in the NaCl-KCl-K2TaF7 melt

International Nuclear Information System (INIS)

Polyakova, L.P.; Kononova, Z.A.; Kremenetskij, V.G.; Polyakov, E.K.

1997-01-01

Using the method of linear voltametry oxygen influence on electrochemical behaviour of tantalum during NaCl-KCl-K 2 TaF 7 melt titration with sodium oxide is studied. It is shown that in NaCl-KCl-K 3 TaOF 6 and NaCl-KCl-K 2 TaF 7 -Na 2 O melts (at molar ratio O/Ta = 1 ) tantalum reduction proceeds from oxyhalide complex of TaOClF 5 -3 composition. On further titration with sodium oxide (1 5 3- complexes, but their concentration is decreased at the cost of formation of insoluble compound K 0,4 TaO 2,4 F 0,6 . When O/Ta ≥ 2,4 tantalum concentration in electrolyte is decreased up to zero and peak of tantalum reduction on voltamogram is not recorded. (author)

The Evolving Role of Physicians - Don't Forget the Generalist Primary Care Providers Comment on "Non-physician Clinicians in Sub-Saharan Africa and the Evolving Role of Physicians".

Science.gov (United States)

Cubaka, Vincent Kalumire; Schriver, Michael; Flinkenflögel, Maaike; Cotton, Philip

2016-06-12

The editorial "Non-physician Clinicians in Sub-Saharan Africa and the Evolving Role of Physicians" by Eyal et al describes non-physician clinicians' (NPC) need for mentorship and support from physicians. We emphasise the same need of support for front line generalist primary healthcare providers who carry out complex tasks yet may have an inadequate skill mix. © 2016 by Kerman University of Medical Sciences.

Cell–cell signaling drives the evolution of complex traits: introduction—lung evo-devo

Science.gov (United States)

Torday, John S.; Rehan, V. K.

2009-01-01

Physiology integrates biology with the environment through cell–cell interactions at multiple levels. The evolution of the respiratory system has been “deconvoluted” (Torday and Rehan in Am J Respir Cell Mol Biol 31:8–12, 2004) through Gene Regulatory Networks (GRNs) applied to cell–cell communication for all aspects of lung biology development, homeostasis, regeneration, and aging. Using this approach, we have predicted the phenotypic consequences of failed signaling for lung development, homeostasis, and regeneration based on evolutionary principles. This cell–cell communication model predicts other aspects of vertebrate physiology as adaptational responses. For example, the oxygen-induced differentiation of alveolar myocytes into alveolar adipocytes was critical for the evolution of the lung in land dwelling animals adapting to fluctuating Phanarezoic oxygen levels over the past 500 million years. Adipocytes prevent lung injury due to oxygen radicals and facilitate the rise of endothermy. In addition, they produce the class I cytokine leptin, which augments pulmonary surfactant activity and alveolar surface area, increasing selection pressure for both respiratory oxygenation and metabolic demand initially constrained by high-systemic vascular pressure, but subsequently compensated by the evolution of the adrenomedullary beta-adrenergic receptor mechanism. Conserted positive selection for the lung and adrenals created further selection pressure for the heart, which becomes progressively more complex phylogenetically in tandem with the lung. Developmentally, increasing heart complexity and size impinges precociously on the gut mesoderm to induce the liver. That evolutionary-developmental interaction is significant because the liver provides regulated sources of glucose and glycogen to the evolving physiologic system, which is necessary for the evolution of the neocortex. Evolution of neocortical control furthers integration of physiologic systems. Such

Quantum chemical DFT study of the interaction between molecular oxygen and FeN₄ complexes, and effect of the macrocyclic ligand.

Science.gov (United States)

Silva, Adilson Luís Pereira; de Almeida, Luciano Farias; Marques, Aldaléa Lopes Brandes; Costa, Hawbertt Rocha; Tanaka, Auro Atsushi; da Silva, Albérico Borges Ferreira; de Jesus Gomes Varela, Jaldyr

2014-03-01

Density functional theory (DFT) was used to examine the interaction between molecular oxygen (O₂) and macrocyclic iron complexes of the type FeN₄ during the formation of FeN₄--O₂ adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O₂ was bonded to iron-tetraaza[14]annulene (FeTAA), iron-tetramethyl-tetraaza[14]annulene (FeTMTAA), iron-hexamethyl-tetraaza[14]annulene (FeHMTAA), iron dibenzotetraaza[14]annulene (FeDBTAA), and two iron-tetramethyl-dibenzotetraaza[14]annulene complexes (FeTMDBTAA1, FeTMDBTAA2). The ground state for FeN₄-O₂ adducts was the open-shell singlet. Analysis of the factors influencing the O₂ bonding process showed that different macrocyclic ligands yielded adducts with differences in O--O and Fe--O₂ bond lengths, total charge over the O₂ fragment, O--O vibrational frequency, and spin density in the O₂ fragment. A smaller energy gap between the α-HOMO of the FeN₄ complexes and the β-LUMO of O₂ increased the interaction between the complex and the O₂ molecule. The order of activity was FeDBTAA < FeTMDBTAA2 < FeTMDBTAA1 < FeTAA < FeTMTAA < FeHMTAA.

Disgust: Evolved function and structure

NARCIS (Netherlands)

Tybur, J.M.; Lieberman, D.; Kurzban, R.; DeScioli, P.

2013-01-01

Interest in and research on disgust has surged over the past few decades. The field, however, still lacks a coherent theoretical framework for understanding the evolved function or functions of disgust. Here we present such a framework, emphasizing 2 levels of analysis: that of evolved function and

The effects of transit time heterogeneity on brain oxygenation during rest and functional activation

Science.gov (United States)

Rasmussen, Peter M; Jespersen, Sune N; Østergaard, Leif

2015-01-01

The interpretation of regional blood flow and blood oxygenation changes during functional activation has evolved from the concept of ‘neurovascular coupling', and hence the regulation of arteriolar tone to meet metabolic demands. The efficacy of oxygen extraction was recently shown to depend on the heterogeneity of capillary flow patterns downstream. Existing compartment models of the relation between tissue metabolism, blood flow, and blood oxygenation, however, typically assume homogenous microvascular flow patterns. To take capillary flow heterogeneity into account, we modeled the effect of capillary transit time heterogeneity (CTH) on the ‘oxygen conductance' used in compartment models. We show that the incorporation of realistic reductions in CTH during functional hyperemia improves model fits to dynamic blood flow and oxygenation changes acquired during functional activation in a literature animal study. Our results support earlier observations that oxygen diffusion properties seemingly change during various physiologic stimuli, and posit that this phenomenon is related to parallel changes in capillary flow patterns. Furthermore, our results suggest that CTH must be taken into account when inferring brain metabolism from changes in blood flow- or blood oxygenation-based signals . PMID:25492112

Sensitivity evaluation of the green alga Chlamydomonas reinhardtii to uranium by pulse amplitude modulated (PAM) fluorometry.

Science.gov (United States)

Herlory, Olivier; Bonzom, Jean-Marc; Gilbin, Rodolphe

2013-09-15

Although ecotoxicological studies tend to address the toxicity thresholds of uranium in freshwaters, there is a lack of information on the effects of the metal on physiological processes, particularly in aquatic plants. Knowing that uranium alters photosynthesis via impairment of the water photo-oxidation process, we determined whether pulse amplitude modulated (PAM) fluorometry was a relevant tool for assessing the impact of uranium on the green alga Chlamydomonas reinhardtii and investigated how and to what extent uranium hampered photosynthetic performance. Photosynthetic activity and quenching were assessed from fluorescence induction curves generated by PAM fluorometry, after 1 and 5h of uranium exposure in controlled conditions. The oxygen-evolving complex (OEC) of PSII was identified as the primary action site of uranium, through alteration of the water photo-oxidation process as revealed by F0/Fv. Limiting re-oxidation of the plastoquinone pool, uranium impaired the electron flux between the photosystems until almost complete inhibition of the PSII quantum efficiency ( [Formula: see text] , EC50=303 ± 64 μg UL(-1) after 5h of exposure) was observed. Non-photochemical quenching (qN) was identified as the most sensitive fluorescence parameter (EC50=142 ± 98 μg UL(-1) after 5h of exposure), indicating that light energy not used in photochemistry was dissipated in non-radiative processes. It was shown that parameters which stemmed from fluorescence induction kinetics are valuable indicators for evaluating the impact of uranium on PSII in green algae. PAM fluorometry provided a rapid and reasonably sensitive method for assessing stress response to uranium in microalgae. Copyright © 2013 Elsevier B.V. All rights reserved.

Evolving dynamics of trading behavior based on coordination game in complex networks

Science.gov (United States)

Bian, Yue-tang; Xu, Lu; Li, Jin-sheng

2016-05-01

This work concerns the modeling of evolvement of trading behavior in stock markets. Based on the assumption of the investors' limited rationality, the evolution mechanism of trading behavior is modeled according to the investment strategy of coordination game in network, that investors are prone to imitate their neighbors' activity through comprehensive analysis on the risk dominance degree of certain investment behavior, the network topology of their relationship and its heterogeneity. We investigate by mean-field analysis and extensive simulations the evolution of investors' trading behavior in various typical networks under different risk dominance degree of investment behavior. Our results indicate that the evolution of investors' behavior is affected by the network structure of stock market and the effect of risk dominance degree of investment behavior; the stability of equilibrium states of investors' behavior dynamics is directly related with the risk dominance degree of some behavior; connectivity and heterogeneity of the network plays an important role in the evolution of the investment behavior in stock market.

Tandem Carbocupration/Oxygenation of Terminal Alkynes

Science.gov (United States)

Zhang, Donghui; Ready, Joseph M.

2008-01-01

A direct and general synthesis of α-branched aldehydes and their enol derivatives is described. Carbocupration of terminal alkynes and subsequent oxygenation with lithium tert-butyl peroxide generates a metallo-enolate. Trapping with various electrophiles provides α-branched aldehydes or stereo-defined trisubstituted enol esters or silyl ethers. The tandem carbocupration/oxygenation tolerates alkyl and silyl ethers, esters and tertiary amines. The reaction is effective with organocopper complexes derived from primary, secondary and tertiary Grignard reagents and from n-butyllithium. PMID:16321021

CARBON CHEMISTRY IN THE ENVELOPE OF VY CANIS MAJORIS: IMPLICATIONS FOR OXYGEN-RICH EVOLVED STARS

International Nuclear Information System (INIS)

Ziurys, L. M.; Tenenbaum, E. D.; Pulliam, R. L.; Woolf, N. J.; Milam, S. N.

2009-01-01

Observations of the carbon-bearing molecules CO, HCN, CS, HNC, CN, and HCO + have been conducted toward the circumstellar envelope of the oxygen-rich red supergiant star, VY Canis Majoris (VY CMa), using the Arizona Radio Observatory (ARO). CO and HCN were also observed toward the O-rich shells of NML Cyg, TX Cam, IK Tau, and W Hya. Rotational transitions of these species at 1 mm, 0.8 mm, and 0.4 mm were measured with the ARO Submillimeter Telescope, including the J = 6 → 5 line of CO at 691 GHz toward TX Cam and W Hya. The ARO 12 m was used for 2 mm and 3 mm observations. Four transitions were observed for HCO + in VY CMa, the first definitive identification of this ion in a circumstellar envelope. Molecular line profiles from VY CMa are complex, indicating three separate outflows: a roughly spherical flow and separate red- and blueshifted winds, as suggested by earlier observations. Spectra from the other sources appear to trace a single outflow component. The line data were modeled with a radiative transfer code to establish molecular abundances relative to H 2 and source distributions. Abundances for CO derived for these objects vary over an order of magnitude, f ∼ 0.4-5 x 10 -4 , with the lower values corresponding to the supergiants. For HCN, a similar range in abundance is found (f ∼ 0.9-9 x 10 -6 ), with no obvious dependence on the mass-loss rate. In VY CMa, HCO + is present in all three outflows with f ∼ 0.4-1.6 x 10 -8 and a spatial extent similar to that of CO. HNC is found only in the red- and blueshifted components with [HCN]/[HNC] ∼ 150-190, while [CN]/[HCN] ∼ 0.01 in the spherical flow. All three velocity components are traced in CS, which has a confined spatial distribution and f ∼ 2-6 x 10 -7 . These observations suggest that carbon-bearing molecules in O-rich shells are produced by a combination of photospheric shocks and photochemistry. Shocks may play a more prominent role in the supergiants because of their macroturbulent

Carbon Chemistry in the Envelope of VY Canis Majoris: Implications for Oxygen-Rich Evolved Stars

Science.gov (United States)

Ziurys, L. M.; Tenenbaum, E. D.; Pulliam, R. L.; Woolf, N. J.; Milam, S. N.

2009-04-01

Observations of the carbon-bearing molecules CO, HCN, CS, HNC, CN, and HCO+ have been conducted toward the circumstellar envelope of the oxygen-rich red supergiant star, VY Canis Majoris (VY CMa), using the Arizona Radio Observatory (ARO). CO and HCN were also observed toward the O-rich shells of NML Cyg, TX Cam, IK Tau, and W Hya. Rotational transitions of these species at 1 mm, 0.8 mm, and 0.4 mm were measured with the ARO Submillimeter Telescope, including the J = 6 → 5 line of CO at 691 GHz toward TX Cam and W Hya. The ARO 12 m was used for 2 mm and 3 mm observations. Four transitions were observed for HCO+ in VY CMa, the first definitive identification of this ion in a circumstellar envelope. Molecular line profiles from VY CMa are complex, indicating three separate outflows: a roughly spherical flow and separate red- and blueshifted winds, as suggested by earlier observations. Spectra from the other sources appear to trace a single outflow component. The line data were modeled with a radiative transfer code to establish molecular abundances relative to H2 and source distributions. Abundances for CO derived for these objects vary over an order of magnitude, f ~ 0.4-5 × 10-4, with the lower values corresponding to the supergiants. For HCN, a similar range in abundance is found (f ~ 0.9-9 × 10-6), with no obvious dependence on the mass-loss rate. In VY CMa, HCO+ is present in all three outflows with f ~ 0.4-1.6 × 10-8 and a spatial extent similar to that of CO. HNC is found only in the red- and blueshifted components with [HCN]/[HNC] ~ 150-190, while [CN]/[HCN] ~ 0.01 in the spherical flow. All three velocity components are traced in CS, which has a confined spatial distribution and f ~ 2-6 × 10-7. These observations suggest that carbon-bearing molecules in O-rich shells are produced by a combination of photospheric shocks and photochemistry. Shocks may play a more prominent role in the supergiants because of their macroturbulent velocities.

Laboratory evaluation of an optimised internet-based speech-in-noise test for occupational high-frequency hearing loss screening: Occupational Earcheck.

Science.gov (United States)

Sheikh Rashid, Marya; Leensen, Monique C J; de Laat, Jan A P M; Dreschler, Wouter A

2017-11-01

The "Occupational Earcheck" (OEC) is a Dutch online self-screening speech-in-noise test developed for the detection of occupational high-frequency hearing loss (HFHL). This study evaluates an optimised version of the test and determines the most appropriate masking noise. The original OEC was improved by homogenisation of the speech material, and shortening the test. A laboratory-based cross-sectional study was performed in which the optimised OEC in five alternative masking noise conditions was evaluated. The study was conducted on 18 normal-hearing (NH) adults, and 15 middle-aged listeners with HFHL. The OEC in a low-pass (LP) filtered stationary background noise (test version LP 3: with a cut-off frequency of 1.6 kHz, and a noise floor of -12 dB) was the most accurate version tested. The test showed a reasonable sensitivity (93%), and specificity (94%) and test reliability (intra-class correlation coefficient: 0.84, mean within-subject standard deviation: 1.5 dB SNR, slope of psychometric function: 13.1%/dB SNR). The improved OEC, with homogenous word material in a LP filtered noise, appears to be suitable for the discrimination between younger NH listeners and older listeners with HFHL. The appropriateness of the OEC for screening purposes in an occupational setting will be studied further.

Oxygen-18 as a tool for studying photorespiration. Oxygen uptake and incorporation into glycolate, glycine and serine

International Nuclear Information System (INIS)

Gerster, R.; Dimon, B.; Tournier, P.; Peybernes, A.

1977-01-01

The intensity of photosynthesis and photorespiration has been determined by measuring 16 O 2 evolvement and 18 O 2 uptake on algae and leaves. In the case of algae, there is still an important oxygen uptake even when ribulose diphosphate oxygenase is inhibited by 10 -3 M cyanide. Oxygen-18 incorporation into glycolate, glycine and serine of photorespiring algae and leaves exposed to atmospheres containing 18 O 2 has also been measured. Only one of the two atoms present in molecular oxygen was incorporated into the carboxyl group of the glycolate excreted from algae; the rate of 18 O incorporation was important (65 to 80% according to experimental conditions), even in the presence of 10 -3 M cyanide. Thus, oxidation of ribulose diphosphate is not the sole reaction leading to 18 O glycolate synthesis. In the case of maize, there was a rapid and important 18 O incorporation into the carboxyl group of glycine and serine, the kinetics of which was determined as a function of CO 2 presence in the atmosphere. These results suggest that photorespiration is also operating in C 4 species. Furthermore, in vitro experiments showed that phosphorylated ceto-acids of the Calvin cycle were very sensitive to H 2 O 2 ; the corresponding reaction can explain O 2 uptake and 18 O labelling of glycolate. (author)

Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

Science.gov (United States)

Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

2007-05-01

Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein.

Oxygen hypothesis of polar gigantism not supported by performance of Antarctic pycnogonids in hypoxia

Science.gov (United States)

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

Late Archean Surface Ocean Oxygenation (Invited)

Science.gov (United States)

Kendall, B.; Reinhard, C.; Lyons, T. W.; Kaufman, A. J.; Anbar, A. D.

2009-12-01

Oxygenic photosynthesis must have evolved by 2.45-2.32 Ga, when atmospheric oxygen abundances first rose above 0.001% present atmospheric level (Great Oxidation Event; GOE). Biomarker evidence for a time lag between the evolution of cyanobacterial oxygenic photosynthesis and the GOE continues to be debated. Geochemical signatures from sedimentary rocks (redox-sensitive trace metal abundances, sedimentary Fe geochemistry, and S isotopes) represent an alternative tool for tracing the history of Earth surface oxygenation. Integrated high-resolution chemostratigraphic profiles through the 2.5 Ga Mt. McRae Shale (Pilbara Craton, Western Australia) suggest a ‘whiff’ of oxygen in the surface environment at least 50 M.y. prior to the GOE. However, the geochemical data from the Mt. McRae Shale does not uniquely constrain the presence or extent of Late Archean ocean oxygenation. Here, we present high-resolution chemostratigraphic profiles from 2.6-2.5 Ga black shales (upper Campbellrand Subgroup, Kaapvaal Craton, South Africa) that provide the earliest direct evidence for an oxygenated ocean water column. On the slope beneath the Campbellrand - Malmani carbonate platform (Nauga Formation), a mildly oxygenated water column (highly reactive iron to total iron ratios [FeHR/FeT] ≤ 0.4) was underlain by oxidizing sediments (low Re and Mo abundances) or mildly reducing sediments (high Re but low Mo abundances). After drowning of the carbonate platform (Klein Naute Formation), the local bottom waters became anoxic (FeHR/FeT > 0.4) and intermittently sulphidic (pyrite iron to highly reactive iron ratios [FePY/FeHR] > 0.8), conducive to enrichment of both Re and Mo in sediments, followed by anoxic and Fe2+-rich (ferruginous) conditions (high FeT, FePY/FeHR near 0). Widespread surface ocean oxygenation is suggested by Re enrichment in the broadly correlative Klein Naute Formation and Mt. McRae Shale, deposited ~1000 km apart in the Griqualand West and Hamersley basins

Toxic and nontoxic components of botulinum neurotoxin complex are evolved from a common ancestral zinc protein

Energy Technology Data Exchange (ETDEWEB)

Inui, Ken [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan); Japan Society for the Promotion of Science, 1-8 Chiyoda-ku, Tokyo 102-8472 (Japan); Sagane, Yoshimasa [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan); Miyata, Keita [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan); Japan Society for the Promotion of Science, 1-8 Chiyoda-ku, Tokyo 102-8472 (Japan); Miyashita, Shin-Ichiro [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan); Suzuki, Tomonori [Department of Bacteriology, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, 2-5-1 Shikata-cho, Kita-ku, Okayama 700-8558 (Japan); Shikamori, Yasuyuki [Agilent Technologies International Japan, Ltd. Takaura-cho 9-1, Hachioji-shi, Tokyo 192-0033 (Japan); Ohyama, Tohru; Niwa, Koichi [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan); Watanabe, Toshihiro, E-mail: t-watana@bioindustry.nodai.ac.jp [Department of Food and Cosmetic Science, Faculty of Bioindustry, Tokyo University of Agriculture, 196 Yasaka, Abashiri 099-2493 (Japan)

2012-03-16

Highlights: Black-Right-Pointing-Pointer BoNT and NTNHA proteins share a similar protein architecture. Black-Right-Pointing-Pointer NTNHA and BoNT were both identified as zinc-binding proteins. Black-Right-Pointing-Pointer NTNHA does not have a classical HEXXH zinc-coordinating motif similar to that found in all serotypes of BoNT. Black-Right-Pointing-Pointer Homology modeling implied probable key residues involved in zinc coordination. -- Abstract: Zinc atoms play an essential role in a number of enzymes. Botulinum neurotoxin (BoNT), the most potent toxin known in nature, is a zinc-dependent endopeptidase. Here we identify the nontoxic nonhemagglutinin (NTNHA), one of the BoNT-complex constituents, as a zinc-binding protein, along with BoNT. A protein structure classification database search indicated that BoNT and NTNHA share a similar domain architecture, comprising a zinc-dependent metalloproteinase-like, BoNT coiled-coil motif and concanavalin A-like domains. Inductively coupled plasma-mass spectrometry analysis demonstrated that every single NTNHA molecule contains a single zinc atom. This is the first demonstration of a zinc atom in this protein, as far as we know. However, the NTNHA molecule does not possess any known zinc-coordinating motif, whereas all BoNT serotypes possess the classical HEXXH motif. Homology modeling of the NTNHA structure implied that a consensus K-C-L-I-K-X{sub 35}-D sequence common among all NTNHA serotype molecules appears to coordinate a single zinc atom. These findings lead us to propose that NTNHA and BoNT may have evolved distinct functional specializations following their branching out from a common ancestral zinc protein.

Oxygen discharge and post-discharge kinetics experiments and modeling for the electric oxygen-iodine laser system.

Science.gov (United States)

Palla, A D; Zimmerman, J W; Woodard, B S; Carroll, D L; Verdeyen, J T; Lim, T C; Solomon, W C

2007-07-26

Laser oscillation at 1315 nm on the I(2P1/2)-->I(2P3/2) transition of atomic iodine has been obtained by a near resonant energy transfer from O2(a1Delta) produced using a low-pressure oxygen/helium/nitric oxide discharge. In the electric discharge oxygen-iodine laser (ElectricOIL) the discharge production of atomic oxygen, ozone, and other excited species adds levels of complexity to the singlet oxygen generator (SOG) kinetics which are not encountered in a classic purely chemical O2(a1Delta) generation system. The advanced model BLAZE-IV has been introduced to study the energy-transfer laser system dynamics and kinetics. Levels of singlet oxygen, oxygen atoms, and ozone are measured experimentally and compared with calculations. The new BLAZE-IV model is in reasonable agreement with O3, O atom, and gas temperature measurements but is under-predicting the increase in O2(a1Delta) concentration resulting from the presence of NO in the discharge and under-predicting the O2(b1Sigma) concentrations. A key conclusion is that the removal of oxygen atoms by NOX species leads to a significant increase in O2(a1Delta) concentrations downstream of the discharge in part via a recycling process; however, there are still some important processes related to the NOX discharge kinetics that are missing from the present modeling. Further, the removal of oxygen atoms dramatically inhibits the production of ozone in the downstream kinetics.

A role for human mitochondrial complex II in the production of reactive oxygen species in human skin

Directory of Open Access Journals (Sweden)

Alasdair Anderson

2014-01-01

Full Text Available The mitochondrial respiratory chain is a major generator of cellular oxidative stress, thought to be an underlying cause of the carcinogenic and ageing process in many tissues including skin. Previous studies of the relative contributions of the respiratory chain (RC complexes I, II and III towards production of reactive oxygen species (ROS have focussed on rat tissues and certainly not on human skin which is surprising as this tissue is regularly exposed to UVA in sunlight, a potent generator of cellular oxidative stress. In a novel approach we have used an array of established specific metabolic inhibitors and DHR123 fluorescence to study the relative roles of the mitochondrial RC complexes in cellular ROS production in 2 types of human skin cells. These include additional enhancement of ROS production by exposure to physiological levels of UVA. The effects within epidermal and dermal derived skin cells are compared to other tissue cell types as well as those harbouring a compromised mitochondrial status (Rho-zero A549. The results show that the complex II inhibitor, TTFA, was the only RC inhibitor to significantly increase UVA-induced ROS production in both skin cell types (P<0.05 suggesting that the role of human skin complex II in terms of influencing ROS production is more important than previously thought particularly in comparison to liver cells. Interestingly, two-fold greater maximal activity of complex II enzyme was observed in both skin cell types compared to liver (P<0.001. The activities of RC enzymes appear to decrease with increasing age and telomere length is correlated with ageing. Our study showed that the level of maximal complex II activity was higher in the MRC5/hTERT (human lung fibroblasts transfected with telomerase cells than the corresponding wild type cells (P=0.0012 which can be considered (in terms of telomerase activity as models of younger and older cells respectively.

TURBULENT OXYGEN FLAMES IN TYPE Ia SUPERNOVAE

International Nuclear Information System (INIS)

Aspden, A. J.; Bell, J. B.; Woosley, S. E.

2011-01-01

In previous studies, we examined turbulence-flame interactions in carbon-burning thermonuclear flames in Type Ia supernovae. In this study, we consider turbulence-flame interactions in the trailing oxygen flames. The two aims of the paper are to examine the response of the inductive oxygen flame to intense levels of turbulence, and to explore the possibility of transition to detonation in the oxygen flame. Scaling arguments analogous to the carbon flames are presented and then compared against three-dimensional simulations for a range of Damkoehler numbers (Da 16 ) at a fixed Karlovitz number. The simulations suggest that turbulence does not significantly affect the oxygen flame when Da 16 16 >1, turbulence enhances heat transfer and drives the propagation of a flame that is narrower than the corresponding inductive flame would be. Furthermore, burning under these conditions appears to occur as part of a combined carbon-oxygen turbulent flame with complex compound structure. The simulations do not appear to support the possibility of a transition to detonation in the oxygen flame, but do not preclude it either.

Planning and complexity : Engaging with temporal dynamics, uncertainty and complex adaptive systems

NARCIS (Netherlands)

Sengupta, Ulysses; Rauws, Ward S.; de Roo, Gert

2016-01-01

The nature of complex systems as a transdisciplinary collection of concepts from physics and economics to sociology and ecology provides an evolving field of inquiry (Laszlo and Krippner, 1998) for urban planning and urban design. As a result, planning theory has assimilated multiple concepts from

Planning and complexity : Engaging with temporal dynamics, uncertainty and complex adaptive systems

NARCIS (Netherlands)

Sengupta, Ulysses; Rauws, Ward S.; de Roo, Gert

The nature of complex systems as a transdisciplinary collection of concepts from physics and economics to sociology and ecology provides an evolving field of inquiry (Laszlo and Krippner, 1998) for urban planning and urban design. As a result, planning theory has assimilated multiple concepts from

Simulating evolution of protein complexes through gene duplication and co-option.

Science.gov (United States)

Haarsma, Loren; Nelesen, Serita; VanAndel, Ethan; Lamine, James; VandeHaar, Peter

2016-06-21

We present a model of the evolution of protein complexes with novel functions through gene duplication, mutation, and co-option. Under a wide variety of input parameters, digital organisms evolve complexes of 2-5 bound proteins which have novel functions but whose component proteins are not independently functional. Evolution of complexes with novel functions happens more quickly as gene duplication rates increase, point mutation rates increase, protein complex functional probability increases, protein complex functional strength increases, and protein family size decreases. Evolution of complexity is inhibited when the metabolic costs of making proteins exceeds the fitness gain of having functional proteins, or when point mutation rates get so large the functional proteins undergo deleterious mutations faster than new functional complexes can evolve. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen, nitric oxide and articular cartilage

Directory of Open Access Journals (Sweden)

B Fermor

2007-04-01

Full Text Available Molecular oxygen is required for the production of nitric oxide (NO, a pro-inflammatory mediator that is associated with osteoarthritis and rheumatoid arthritis. To date there has been little consideration of the role of oxygen tension in the regulation of nitric oxide production associated with arthritis. Oxygen tension may be particularly relevant to articular cartilage since it is avascular and therefore exists at a reduced oxygen tension. The superficial zone exists at approximately 6% O2, while the deep zone exists at less than 1% O2. Furthermore, oxygen tension can alter matrix synthesis, and the material properties of articular cartilage in vitro.The increase in nitric oxide associated with arthritis can be caused by pro-inflammatory cytokines and mechanical stress. Oxygen tension significantly alters endogenous NO production in articular cartilage, as well as the stimulation of NO in response to both mechanical loading and pro-inflammatory cytokines. Mechanical loading and pro-inflammatory cytokines also increase the production of prostaglandin E2 (PGE2. There is a complex interaction between NO and PGE2, and oxygen tension can alter this interaction. These findings suggest that the relatively low levels of oxygen within the joint may have significant influences on the metabolic activity, and inflammatory response of cartilage as compared to ambient levels. A better understanding of the role of oxygen in the production of inflammatory mediators in response to mechanical loading, or pro-inflammatory cytokines, may aid in the development of strategies for therapeutic intervention in arthritis.

Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

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Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

2016-06-20

Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

Evolved H II regions

International Nuclear Information System (INIS)

Churchwell, E.

1975-01-01

A probable evolutionary sequence of H II regions based on six distinct types of observed objects is suggested. Two examples which may deviate from this idealized sequence, are discussed. Even though a size-mean density relation of H II regions can be used as a rough indication of whether a nebula is very young or evolved, it is argued that such a relation is not likely to be useful for the quantitative assignment of ages to H II regions. Evolved H II regions appear to fit into one of four structural types: rings, core-halos, smooth structures, and irregular or filamentary structures. Examples of each type are given with their derived physical parameters. The energy balance in these nebulae is considered. The mass of ionized gas in evolved H II regions is in general too large to trace the nebula back to single compact H II regions. Finally, the morphological type of the Galaxy is considered from its H II region content. 2 tables, 2 figs., 29 refs

Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

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Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

Peripheral Nerve Injuries and Transplantation of Olfactory Ensheathing Cells for Axonal Regeneration and Remyelination: Fact or Fiction?

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Christine Radtke

2012-10-01

Full Text Available Successful nerve regeneration after nerve trauma is not only important for the restoration of motor and sensory functions, but also to reduce the potential for abnormal sensory impulse generation that can occur following neuroma formation. Satisfying functional results after severe lesions are difficult to achieve and the development of interventional methods to achieve optimal functional recovery after peripheral nerve injury is of increasing clinical interest. Olfactory ensheathing cells (OECs have been used to improve axonal regeneration and functional outcome in a number of studies in spinal cord injury models. The rationale is that the OECs may provide trophic support and a permissive environment for axonal regeneration. The experimental transplantation of OECs to support and enhance peripheral nerve regeneration is much more limited. This chapter reviews studies using OECs as an experimental cell therapy to improve peripheral nerve regeneration.

Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

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Morales, Javier; Günther, Germán; Zanocco, Antonio L; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

Directory of Open Access Journals (Sweden)

Javier Morales

Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

Active oxygen doctors the evidence

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Castelló, Ana; Francès, Francesc; Corella, Dolores; Verdú, Fernando

2009-02-01

Investigation at the scene of a crime begins with the search for clues. In the case of bloodstains, the most frequently used reagents are luminol and reduced phenolphthalein (or phenolphthalin that is also known as the Kastle-Meyer colour test). The limitations of these reagents have been studied and are well known. Household cleaning products have evolved with the times, and new products with active oxygen are currently widely used, as they are considered to be highly efficient at removing all kinds of stains on a wide range of surfaces. In this study, we investigated the possible effects of these new cleaning products on latent bloodstains that may be left at a scene of a crime. To do so, various fabrics were stained with blood and then washed using cleaning agents containing active oxygen. The results of reduced phenolphthalein, luminol and human haemoglobin tests on the washed fabrics were negative. The conclusion is that these new products alter blood to such an extent that it can no longer be detected by currently accepted methods employed in criminal investigations. This inability to locate bloodstains means that highly important evidence (e.g. a DNA profile) may be lost. Consequently, it is important that investigators are aware of this problem so as to compensate for it.

Remyelination of the injured spinal cord

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Sasaki, Masanori; Li, Bingcang; Lankford, Karen L.; Radtke, Christine; Kocsis, Jeffery D.

2008-01-01

Contusive spinal cord injury (SCI) can result in necrosis of the spinal cord, but often long white matter tracts outside of the central necrotic core are demyelinated. One experimental strategy to improve functional outcome following SCI is to transplant myelin-forming cells to remyelinate these axons and improve conduction. This review focuses on transplantation studies using olfactory ensheathing cell (OEC) to improve functional outcome in experimental models of SCI and demyelination. The biology of the OEC, and recent experimental research and clinical studies using OECs as a potential cell therapy candidate are discussed. PMID:17618995

Manipulating Endothelial Progenitor Cell Homing with Sphingosine-1-Phosphate for Terapeutic Angiogenesis

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Williams, Priscilla Anne

Ischemic vascular diseases are the main cause of mortality worldwide and yet current therapies only delay disease progression and improve quality of life without addressing the fundamental problem of tissue loss. Within the field of tissue engineering, therapeutic angiogenesis provides a promising approach to alternatively provide new blood vessel formation via spatiotemporally controlled delivery of proangiogenic agents. Sphingosine-1-phosphate (S1P), a bioactive lysophospholipid that is upregulated under ischemic conditions, has recently gained great enthusiasm as a potential mediator in neovascularization strategies given its essential roles in promoting both neovessel formation and stabilization, and cellular trafficking along highly regulated endogenous gradients. Herein, the governing hypothesis guiding this dissertation is that local biomaterial-controlled delivery of S1P may be used to enhance migration and recruitment of vascular progenitor cells for enhanced therapeutic angiogenesis within ischemic tissue. The initial work in this dissertation investigated the effect of hypoxia on the angiogenic response of both mature and progenitor endothelial cells to S1P stimulation in vitro. Outgrowth endothelial cells (OECs) were isolated from human umbilical cord blood to provide a clinically relevant source of vascular progenitor cells for the studies conducted within this dissertation. S1P stimulation promoted angiogenic activity of both ECs and OECs under both ambient and hypoxic (1%) oxygen tensions. Furthermore, dual therapy with the combination of S1P and vascular endothelial growth factor (VEGF) further enhanced cellular responses. Interestingly, hypoxia substantially augmented the functional response of OECs to S1P, resulting in 25-fold and 6.5-fold increases in directed migration and sprouting, respectively. Thus, these studies highlighted the potential for S1P as a therapeutic agent for treatment of ischemic diseases. An injectable biomaterial system

Hyperbaric Oxygen Environment Can Enhance Brain Activity and Multitasking Performance

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Dor Vadas

2017-09-01

Full Text Available Background: The Brain uses 20% of the total oxygen supply consumed by the entire body. Even though, <10% of the brain is active at any given time, it utilizes almost all the oxygen delivered. In order to perform complex tasks or more than one task (multitasking, the oxygen supply is shifted from one brain region to another, via blood perfusion modulation. The aim of the present study was to evaluate whether a hyperbaric oxygen (HBO environment, with increased oxygen supply to the brain, will enhance the performance of complex and/or multiple activities.Methods: A prospective, double-blind randomized control, crossover trial including 22 healthy volunteers. Participants were asked to perform a cognitive task, a motor task and a simultaneous cognitive-motor task (multitasking. Participants were randomized to perform the tasks in two environments: (a normobaric air (1 ATA 21% oxygen (b HBO (2 ATA 100% oxygen. Two weeks later participants were crossed to the alternative environment. Blinding of the normobaric environment was achieved in the same chamber with masks on while hyperbaric sensation was simulated by increasing pressure in the first minute and gradually decreasing to normobaric environment prior to tasks performance.Results: Compared to the performance at normobaric conditions, both cognitive and motor single tasks scores were significantly enhanced by HBO environment (p < 0.001 for both. Multitasking performance was also significantly enhanced in HBO environment (p = 0.006 for the cognitive part and p = 0.02 for the motor part.Conclusions: The improvement in performance of both single and multi-tasking while in an HBO environment supports the hypothesis which according to, oxygen is indeed a rate limiting factor for brain activity. Hyperbaric oxygenation can serve as an environment for brain performance. Further studies are needed to evaluate the optimal oxygen levels for maximal brain performance.

Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

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Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

2008-12-18

A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.

Sensitivity of clostridium acetobutylicum to oxygen and ionizing radiation

International Nuclear Information System (INIS)

Sozer, A.C.; Adler, H.I.; Machanoff, R.; Haney, S.

1984-01-01

The authors are studying the sensitivity of four strains of the obligate anaerobe, Clostridium acetobutylicum, to oxygen and ionizing radiation. Anaerobic bacteria are useful for such studies because of the absence of elaborate oxygen detoxification mechanisms that are found in aerobes. Their experiments make use of sterile membrane fragments from Escherichia coli that rapidly remove molecular oxygen from media and permit growth of anaerobes without the use of reducing agents or anaerobic chambers. Of the four strains examined for sensitivity to ionizing radiation under anaerobic conditions, one has an LD/sub 50/ of -- 25 krads and the others have an LD/sub 50/ of -- 7 krads. The radiation resistant strain is also relatively resistant to oxygen exposure. Sensitivity to oxygen was determined by diluting cells in buffer at 28 0 and bubbling with air. An exposure to air for 40 min induced only slight inactivation in the radiation resistant strain. All strains are capable of removing oxygen from complex media but there is no apparent correlation between this oxygen consuming reaction and inactivation by either oxygen or radiation

Evolving Technologies: A View to Tomorrow

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Tamarkin, Molly; Rodrigo, Shelley

2011-01-01

Technology leaders must participate in strategy creation as well as operational delivery within higher education institutions. The future of higher education--the view to tomorrow--is irrevocably integrated and intertwined with evolving technologies. This article focuses on two specific evolving technologies: (1) alternative IT sourcing; and (2)…

Pulmonary Sporotrichosis: An Evolving Clinical Paradigm.

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Aung, Ar K; Spelman, Denis W; Thompson, Philip J

2015-10-01

In recent decades, sporotrichosis, caused by thermally dimorphic fungi Sporothrix schenckii complex, has become an emerging infection in many parts of the world. Pulmonary infection with S. schenckii still remains relatively uncommon, possibly due to underrecognition. Pulmonary sporotrichosis presents with distinct clinical and radiological patterns in both immunocompetent and immunocompromised hosts and can often result in significant morbidity and mortality despite treatment. Current understanding regarding S. schenckii biology, epidemiology, immunopathology, clinical diagnostics, and treatment options has been evolving in the recent years with increased availability of molecular sequencing techniques. However, this changing knowledge has not yet been fully translated into a better understanding of the clinical aspects of pulmonary sporotrichosis, as such current management guidelines remain unsupported by high-level clinical evidence. This article examines recent advances in the knowledge of sporotrichosis and its application to the difficult challenges of managing pulmonary sporotrichosis. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

A local-world evolving hypernetwork model

International Nuclear Information System (INIS)

Yang Guang-Yong; Liu Jian-Guo

2014-01-01

Complex hypernetworks are ubiquitous in the real system. It is very important to investigate the evolution mechanisms. In this paper, we present a local-world evolving hypernetwork model by taking into account the hyperedge growth and local-world hyperedge preferential attachment mechanisms. At each time step, a newly added hyperedge encircles a new coming node and a number of nodes from a randomly selected local world. The number of the selected nodes from the local world obeys the uniform distribution and its mean value is m. The analytical and simulation results show that the hyperdegree approximately obeys the power-law form and the exponent of hyperdegree distribution is γ = 2 + 1/m. Furthermore, we numerically investigate the node degree, hyperedge degree, clustering coefficient, as well as the average distance, and find that the hypernetwork model shares the scale-free and small-world properties, which shed some light for deeply understanding the evolution mechanism of the real systems. (interdisciplinary physics and related areas of science and technology)

Kinetics and mechanisms of the oxidation of alcohols and hydroxylamines by hydrogen peroxide, catalyzed by methyltrioxorhenium, MTO, and the oxygen binding properties of cobalt Schiff base complexes

Energy Technology Data Exchange (ETDEWEB)

Zauche, Timothy [Iowa State Univ., Ames, IA (United States)

1999-02-12

Catalysis is a very interesting area of chemistry, which is currently developing at a rapid pace. A great deal of effort is being put forth by both industry and academia to make reactions faster and more productive. One method of accomplishing this is by the development of catalysts. Enzymes are an example of catalysts that are able to perform reactions on a very rapid time scale and also very specifically; a goal for every man-made catalyst. A kinetic study can also be carried out for a reaction to gain a better understanding of its mechanism and to determine what type of catalyst would assist the reaction. Kinetic studies can also help determine other factors, such as the shelf life of a chemical, or the optimum temperature for an industrial scale reaction. An area of catalysis being studied at this time is that of oxygenations. Life on this earth depends on the kinetic barriers for oxygen in its various forms. If it were not for these barriers, molecular oxygen, water, and the oxygenated materials in the land would be in a constant equilibrium. These same barriers must be overcome when performing oxygenation reactions on the laboratory or industrial scale. By performing kinetic studies and developing catalysts for these reactions, a large number of reactions can be made more economical, while making less unwanted byproducts. For this dissertation the activation by transition metal complexes of hydrogen peroxide or molecular oxygen coordination will be discussed.

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

International Nuclear Information System (INIS)

Berg, Danielle A.; Skillman, Evan D.; Marble, Andrew R.

2011-01-01

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 B luminosity-metallicity relation. Our new observations extend the wavelength coverage to include the [O II] λλ3726, 3729 doublet, which adds leverage in oxygen abundance estimates and allows measurements of N/O ratios. All four spectra are low excitation, with relatively high N/O ratios (N/O ∼> 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.

Comparative evolutionary analysis of protein complexes in E. coli and yeast

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Ranea Juan AG

2010-02-01

Full Text Available Abstract Background Proteins do not act in isolation; they frequently act together in protein complexes to carry out concerted cellular functions. The evolution of complexes is poorly understood, especially in organisms other than yeast, where little experimental data has been available. Results We generated accurate, high coverage datasets of protein complexes for E. coli and yeast in order to study differences in the evolution of complexes between these two species. We show that substantial differences exist in how complexes have evolved between these organisms. A previously proposed model of complex evolution identified complexes with cores of interacting homologues. We support findings of the relative importance of this mode of evolution in yeast, but find that it is much less common in E. coli. Additionally it is shown that those homologues which do cluster in complexes are involved in eukaryote-specific functions. Furthermore we identify correlated pairs of non-homologous domains which occur in multiple protein complexes. These were identified in both yeast and E. coli and we present evidence that these too may represent complex cores in yeast but not those of E. coli. Conclusions Our results suggest that there are differences in the way protein complexes have evolved in E. coli and yeast. Whereas some yeast complexes have evolved by recruiting paralogues, this is not apparent in E. coli. Furthermore, such complexes are involved in eukaryotic-specific functions. This implies that the increase in gene family sizes seen in eukaryotes in part reflects multiple family members being used within complexes. However, in general, in both E. coli and yeast, homologous domains are used in different complexes.

Spacetimes containing slowly evolving horizons

International Nuclear Information System (INIS)

Kavanagh, William; Booth, Ivan

2006-01-01

Slowly evolving horizons are trapping horizons that are ''almost'' isolated horizons. This paper reviews their definition and discusses several spacetimes containing such structures. These include certain Vaidya and Tolman-Bondi solutions as well as (perturbatively) tidally distorted black holes. Taking into account the mass scales and orders of magnitude that arise in these calculations, we conjecture that slowly evolving horizons are the norm rather than the exception in astrophysical processes that involve stellar-scale black holes

The protective effect of curcumin in Olfactory Ensheathing Cells exposed to hypoxia.

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Bonfanti, Roberta; Musumeci, Teresa; Russo, Cristina; Pellitteri, Rosalia

2017-02-05

Curcumin, a phytochemical component derived from the rhizomes of Curcuma longa, has shown a great variety of pharmacological activities, such as anti-inflammatory, anti-tumor, anti-depression and anti-oxidant activity. Therefore, in the last years it has been used as a therapeutic agent since it confers protection in different neurodegenerative diseases, cerebral ischemia and excitotoxicity. Olfactory Ensheathing Cells (OECs) are glial cells of the olfactory system. They are able to secrete several neurotrophic growth factors, promote axonal growth and support the remyelination of damaged axons. OEC transplantation has emerged as a possible experimental therapy to induce repair of spinal cord injury, even if the functional recovery is still limited. Since hypoxia is a secondary effect in spinal cord injury, this in vitro study investigates the protective effect of curcumin in OECs exposed to hypoxia. Primary OECs were obtained from neonatal rat olfactory bulbs and placed both in normal and hypoxic conditions. Furthermore, some cells were grown with basic Fibroblast Growth Factor (bFGF) and/or curcumin at different concentration and times. The results obtained through immunocytochemical procedures and MTT test show that curcumin stimulates cell viability in OECs grown in normal and hypoxic conditions. Furthermore, the synergistic effect of curcumin and bFGF is the most effective exerting protection on OECs. Since spinal cord injury is often accompanied by secondary insults, such as ischemia or hypoxia, our results suggest that curcumin in combination with bFGF might be considered a possible approach for restoration in injuries. Copyright © 2016 Elsevier B.V. All rights reserved.

Clinical, radiological, surgical, and pathological determinants of olfactory groove schwannoma

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Andi Sadayandi Ramesh

2014-01-01

Full Text Available Background: Olfactory groove schwannomas (OGS are rare anterior cranial fossa base tumors with only 41 cases reported in literature. Olfactory ensheathing cell schwannoma (OECS has similar clinico-radiological features as OGS, but a different cell of origin. In recent years, there is growing interest in OECS as more cases are being reported. Aims: The objective was to study the clinico-radiological features of OGS and define the histological differentiation from OECS. Materials and Methods: We retrospectively analyzed clinical, radiological, surgical and histopathological picture of all cases of OGS managed in our institute. Immuno histochemical studies were performed in these tumors for differentiating from OECS. A comprehensive review of articles published until date describing the operative treatment was done. Results: All three cases had presented with seizures, two had anosmia and papilledema. Gross-total resection was achieved in all our patients. One patient expired in the postoperative period due to septicemia. Positive expression to newer immuno histochemical biomarker CD57 (Leu7, with negative staining to smooth muscle α-actin (SMA was helpful in confirming the diagnosis of OGS and differentiating it from OECS in all our cases. Conclusions: OECS, though rare has to be differentiated from OGS using immuno histochemistry. Gross-total resection of OGS with preservation of olfactory function is often possible and curative. Although these tumors are commonly treated with microsurgical skull base approaches, an endoscopic endonasal approach can be considered in some cases, with repair using mucoperiosteal pedicled flap to prevent cerebrospinal fluid leak.

Evolving Concepts of Asthma

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Ray, Anuradha; Wenzel, Sally E.

2015-01-01

Our understanding of asthma has evolved over time from a singular disease to a complex of various phenotypes, with varied natural histories, physiologies, and responses to treatment. Early therapies treated most patients with asthma similarly, with bronchodilators and corticosteroids, but these therapies had varying degrees of success. Similarly, despite initial studies that identified an underlying type 2 inflammation in the airways of patients with asthma, biologic therapies targeted toward these type 2 pathways were unsuccessful in all patients. These observations led to increased interest in phenotyping asthma. Clinical approaches, both biased and later unbiased/statistical approaches to large asthma patient cohorts, identified a variety of patient characteristics, but they also consistently identified the importance of age of onset of disease and the presence of eosinophils in determining clinically relevant phenotypes. These paralleled molecular approaches to phenotyping that developed an understanding that not all patients share a type 2 inflammatory pattern. Using biomarkers to select patients with type 2 inflammation, repeated trials of biologics directed toward type 2 cytokine pathways saw newfound success, confirming the importance of phenotyping in asthma. Further research is needed to clarify additional clinical and molecular phenotypes, validate predictive biomarkers, and identify new areas for possible interventions. PMID:26161792

Oxygen, ecology, and the Cambrian radiation of animals

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Sperling, Erik A.; Frieder, Christina A.; Raman, Akkur V.; Girguis, Peter R.; Levin, Lisa A.; Knoll, Andrew H.

2013-08-01

The Proterozoic-Cambrian transition records the appearance of essentially all animal body plans (phyla), yet to date no single hypothesis adequately explains both the timing of the event and the evident increase in diversity and disparity. Ecological triggers focused on escalatory predator-prey "arms races" can explain the evolutionary pattern but not its timing, whereas environmental triggers, particularly ocean/atmosphere oxygenation, do the reverse. Using modern oxygen minimum zones as an analog for Proterozoic oceans, we explore the effect of low oxygen levels on the feeding ecology of polychaetes, the dominant macrofaunal animals in deep-sea sediments. Here we show that low oxygen is clearly linked to low proportions of carnivores in a community and low diversity of carnivorous taxa, whereas higher oxygen levels support more complex food webs. The recognition of a physiological control on carnivory therefore links environmental triggers and ecological drivers, providing an integrated explanation for both the pattern and timing of Cambrian animal radiation.

Photosensitized production of singlet oxygen: spatially-resolved optical studies in single cells

DEFF Research Database (Denmark)

Breitenbach, Thomas; Kuimova, Marina; Gbur, Peter

2009-01-01

be monitored using viability assays. Time- and spatially-resolved optical measurements of both singlet oxygen and its precursor, the excited state sensitizer, reflect the complex and dynamic morphology of the cell. These experiments help elucidate photoinduced, oxygen-dependent events that compromise cell...

Cross-sectional evaluation of an internet-based hearing screening test in an occupational setting

NARCIS (Netherlands)

Sheikh Rashid, Marya; Leensen, Monique Cj; de Laat, Jan Apm; Dreschler, Wouter A.

2017-01-01

Objectives The Occupational Earcheck (OEC) is an online internet test to detect high-frequency hearing loss for the purposes of occupational hearing screening. In this study, we evaluated the OEC in an occupational setting in order to assess test sensitivity, specificity, and validity. Methods A

Transplantation of olfactory ensheathing cells as adjunct cell therapy for peripheral nerve injury.

Science.gov (United States)

Radtke, Christine; Wewetzer, Konstantin; Reimers, Kerstin; Vogt, Peter M

2011-01-01

Traumatic events, such as work place trauma or motor vehicle accident violence, result in a significant number of severe peripheral nerve lesions, including nerve crush and nerve disruption defects. Transplantation of myelin-forming cells, such as Schwann cells (SCs) or olfactory ensheathing cells (OECs), may be beneficial to the regenerative process because the applied cells could mediate neurotrophic and neuroprotective effects by secretion of chemokines. Moreover, myelin-forming cells are capable of bridging the repair site by establishing an environment permissive to axonal regeneration. The cell types that are subject to intense investigation include SCs and OECs either derived from the olfactory bulb or the olfactory mucosa, stromal cells from bone marrow (mesenchymal stem cells, MSCs), and adipose tissue-derived cells. OECs reside in the peripheral and central nervous system and have been suggested to display unique regenerative properties. However, so far OECs were mainly used in experimental studies to foster central regeneration and it was not until recently that their regeneration-promoting activity for the peripheral nervous system was recognized. In the present review, we summarize recent experimental evidence regarding the regenerative effects of OECs applied to the peripheral nervous system that may be relevant to design novel autologous cell transplantation therapies. © 2011 Cognizant Comm. Corp.

Gastric Ulcers in Middle-Aged Rats: The Healing Effect of Essential Oil from Citrus aurantium L. (Rutaceae

Directory of Open Access Journals (Sweden)

C. M. Polo

2012-01-01

Full Text Available The elderly population has experienced increased life expectancy as well as the increased incidence of gastric ulcers. The peels of fruits from Citrus aurantium L., popularly known in Brazil as orange bitter, are commonly used asatea form for the treatment of gastrointestinal tract disorders, such as ulcer and gastritis. We evaluated the healing effects of essential oil from the peels of Citrus aurantium fruits (OEC on gastric ulcers in middle-aged rats. We examined the effects of a 14-day chronic OEC treatment on gastric mucosa in middle-aged male Wistar rats that were given acetic-acid-induced gastric lesions by morphometric and immunohistological analyses. Oral OEC treatment significantly reduced the lesion area (76% within the gastric mucosa and significantly increased (P<.05 the height of regenerated mucosa (59% when compared to the negative control group. Immunohistochemical analysis of the molecular markers such as COX-2, HSP-70, VEGF, and PCNA in the gastric mucosa confirmed that OEC treatment induced healing effects by increasing the number of new blood vessels and by augmenting gastric mucus in the mucosa glands. These results suggest that the oil from Citrus aurantium effectively heals gastric ulcers in middle-aged animals; however, safe use of OEC demands special care and precautions.

Online epistemic communities: theoretical and methodological directions for understanding knowledge co-elaboration in new digital spaces.

Science.gov (United States)

Détienne, Françoise; Barcellini, Flore; Baker, Michael; Burkhardt, Jean-Marie; Fréard, Dominique

2012-01-01

This paper presents, illustrates and discusses a generic framework for studying knowledge co-elaboration in online epistemic communities ("OECs"). Our approach is characterised by: considering knowledge co-elaboration as a design activity; distinguishing discussion and production spaces in OECs; characterising participation via the notion of role; fine-grained analyses of meaning, content and communicative functions in interactions. On this basis, three key issues for ergonomics research on OECs are discussed and illustrated by results from our previous studies on OSS and Wikipedia. One issue concerns the interrelation between design (task) and regulation. Whereas design task-oriented activity is distributed among participants, we illustrate that OCEs function with specialised emerging roles of group regulation. However, the task-oriented activity also functions at an interpersonal level, as an interplay of knowledge-based discussion with negotiation of competencies. Another issue concerns the foci of activity on the (designed) knowledge object. Based on a generic task model, we illustrate asymmetry and distinctiveness in tasks' foci of participants. The last issue concerns how design-use mediation is ensured by specific forms of mediation roles in OECs. Finally we discuss the degree of generality of our framework and draw some perspectives for extending our framework to other OECs.

An atomistic vision of the Mass Action Law: Prediction of carbon/oxygen defects in silicon

Energy Technology Data Exchange (ETDEWEB)

Brenet, G.; Timerkaeva, D.; Caliste, D.; Pochet, P. [CEA, INAC-SP2M, Atomistic Simulation Laboratory, F-38000 Grenoble (France); Univ. Grenoble Alpes, INAC-SP2M, L-Sim, F-38000 Grenoble (France); Sgourou, E. N.; Londos, C. A. [University of Athens, Solid State Physics Section, Panepistimiopolis Zografos, Athens 157 84 (Greece)

2015-09-28

We introduce an atomistic description of the kinetic Mass Action Law to predict concentrations of defects and complexes. We demonstrate in this paper that this approach accurately predicts carbon/oxygen related defect concentrations in silicon upon annealing. The model requires binding and migration energies of the impurities and complexes, here obtained from density functional theory (DFT) calculations. Vacancy-oxygen complex kinetics are studied as a model system during both isochronal and isothermal annealing. Results are in good agreement with experimental data, confirming the success of the methodology. More importantly, it gives access to the sequence of chain reactions by which oxygen and carbon related complexes are created in silicon. Beside the case of silicon, the understanding of such intricate reactions is a key to develop point defect engineering strategies to control defects and thus semiconductors properties.

Olfactory ensheathing cell transplantation for spinal cord injury: An 18-year bibliometric analysis based on the Web of Science.

Science.gov (United States)

Leng, Zikuan; He, Xijing; Li, Haopeng; Wang, Dong; Cao, Kai

2013-05-15

Olfactory ensheathing cell (OEC) transplantation is a promising new approach for the treatment of spinal cord injury (SCI), and an increasing number of scientific publications are devoted to this treatment strategy. This bibliometric analysis was conducted to assess global research trends in OEC transplantation for SCI. All of the data in this study originate from the Web of Science maintained by the Institute for Scientific Information, USA, and includes SCI-EXPANDED, SSCI, A&HCI, CPCI-S, CPCI-SSH, BKCI-S, BKCI-SSH, CCR-EXPANDED and IC. The Institute for Scientific Information's Web of Science was searched using the keywords "olfactory ensheathing cells" or "OECs" or "olfactory ensheathing glia" or "OEG" or "olfactory ensheathing glial cells" or "OEGs" and "spinal cord injury" or "SCI" or "spinal injury" or "spinal transection" for literature published from January 1898 to May 2012. Original articles, reviews, proceedings papers and meeting abstracts, book chapters and editorial materials on OEC transplantation for SCI were included. Simultaneously, unpublished literature and literature for which manual information retrieval was required were excluded. ALL SELECTED LITERATURES ADDRESSING OEC TRANSPLANTATION FOR SCI WERE EVALUATED IN THE FOLLOWING ASPECTS: publication year, document type, language, author, institution, times cited, Web of Science category, core source title, countries/territories and funding agency. In the Web of Science published by the Institute for Scientific Information, the earliest literature record was in April, 1995. Four hundred and fourteen publications addressing OEC transplantation for SCI were added to the data library in the past 18 years, with an annually increasing trend. Of 415 records, 405 publications were in English. Two hundred and fifty-nine articles ranked first in the distribution of document type, followed by 141 reviews. Thirty articles and 20 reviews, cited more than 55 times by the date the publication data were

Whole-genome sequencing of a laboratory-evolved yeast strain

Directory of Open Access Journals (Sweden)

Dunham Maitreya J

2010-02-01

Full Text Available Abstract Background Experimental evolution of microbial populations provides a unique opportunity to study evolutionary adaptation in response to controlled selective pressures. However, until recently it has been difficult to identify the precise genetic changes underlying adaptation at a genome-wide scale. New DNA sequencing technologies now allow the genome of parental and evolved strains of microorganisms to be rapidly determined. Results We sequenced >93.5% of the genome of a laboratory-evolved strain of the yeast Saccharomyces cerevisiae and its ancestor at >28× depth. Both single nucleotide polymorphisms and copy number amplifications were found, with specific gains over array-based methodologies previously used to analyze these genomes. Applying a segmentation algorithm to quantify structural changes, we determined the approximate genomic boundaries of a 5× gene amplification. These boundaries guided the recovery of breakpoint sequences, which provide insights into the nature of a complex genomic rearrangement. Conclusions This study suggests that whole-genome sequencing can provide a rapid approach to uncover the genetic basis of evolutionary adaptations, with further applications in the study of laboratory selections and mutagenesis screens. In addition, we show how single-end, short read sequencing data can provide detailed information about structural rearrangements, and generate predictions about the genomic features and processes that underlie genome plasticity.

Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

Science.gov (United States)

Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

Evolving phenotypic networks in silico.

Science.gov (United States)

François, Paul

2014-11-01

Evolved gene networks are constrained by natural selection. Their structures and functions are consequently far from being random, as exemplified by the multiple instances of parallel/convergent evolution. One can thus ask if features of actual gene networks can be recovered from evolutionary first principles. I review a method for in silico evolution of small models of gene networks aiming at performing predefined biological functions. I summarize the current implementation of the algorithm, insisting on the construction of a proper "fitness" function. I illustrate the approach on three examples: biochemical adaptation, ligand discrimination and vertebrate segmentation (somitogenesis). While the structure of the evolved networks is variable, dynamics of our evolved networks are usually constrained and present many similar features to actual gene networks, including properties that were not explicitly selected for. In silico evolution can thus be used to predict biological behaviours without a detailed knowledge of the mapping between genotype and phenotype. Copyright © 2014 The Author. Published by Elsevier Ltd.. All rights reserved.

canEvolve: a web portal for integrative oncogenomics.

Directory of Open Access Journals (Sweden)

Mehmet Kemal Samur

Full Text Available BACKGROUND & OBJECTIVE: Genome-wide profiles of tumors obtained using functional genomics platforms are being deposited to the public repositories at an astronomical scale, as a result of focused efforts by individual laboratories and large projects such as the Cancer Genome Atlas (TCGA and the International Cancer Genome Consortium. Consequently, there is an urgent need for reliable tools that integrate and interpret these data in light of current knowledge and disseminate results to biomedical researchers in a user-friendly manner. We have built the canEvolve web portal to meet this need. RESULTS: canEvolve query functionalities are designed to fulfill most frequent analysis needs of cancer researchers with a view to generate novel hypotheses. canEvolve stores gene, microRNA (miRNA and protein expression profiles, copy number alterations for multiple cancer types, and protein-protein interaction information. canEvolve allows querying of results of primary analysis, integrative analysis and network analysis of oncogenomics data. The querying for primary analysis includes differential gene and miRNA expression as well as changes in gene copy number measured with SNP microarrays. canEvolve provides results of integrative analysis of gene expression profiles with copy number alterations and with miRNA profiles as well as generalized integrative analysis using gene set enrichment analysis. The network analysis capability includes storage and visualization of gene co-expression, inferred gene regulatory networks and protein-protein interaction information. Finally, canEvolve provides correlations between gene expression and clinical outcomes in terms of univariate survival analysis. CONCLUSION: At present canEvolve provides different types of information extracted from 90 cancer genomics studies comprising of more than 10,000 patients. The presence of multiple data types, novel integrative analysis for identifying regulators of oncogenesis, network

Measurement of oxygen thermomigration in a hypostoichiometric mixed oxide

International Nuclear Information System (INIS)

Norris, D.I.R.; Coleman, S.C.; Kay, P.

1978-08-01

A method of determining oxygen to metal ratios in hypostoichiometric (U, Ce)Osub(2-x) by means of lattice parameter measurement and its application to thermomigration experiments is described. The technique is shown to compare favourably with other methods when a simple structure prevails. It is found that oxygen redistributes down an imposed temperature gradient, confirming theoretical predictions, and that the measured Arrhenius slope decreases as the cerium valency decreases. This effect is more marked than in (U, Pu)Osub(2-x). The results are attributable to solid state transport of oxygen vacancies and suggest that immobile complexes incorporating some oxygen deficiency are more easily formed in (U, Ce)Osub(2-x) than in (U, Pu)Osub(2-x). (author)

Oxygen effect on the electrical characteristics of pentacene transistors

International Nuclear Information System (INIS)

Hu Yan; Dong Guifang; Hu Yuanchuan; Wang Liduo; Qiu Yong

2006-01-01

The effect of oxygen on the electrical characteristics of organic thin film transistors with pentacene as the active layer has been investigated. The saturation currents and mobilities of the transistors increase as the ambient oxygen concentration decreases, which is ascribed to the formation of a charge transfer complex between pentacene and O 2 . The deposition rate of the pentacene layer affects this phenomenon. The transistor with the pentacene layer deposited at a rate of 15 nm min -1 shows higher sensitivity to oxygen concentration than the device with the pentacene layer deposited at 30 nm min -1 . We suggest that when deposited at a lower rate the pentacene film is less compact, leading to easier entrance of oxygen into the charge accumulation region

Management of complex dynamical systems

Science.gov (United States)

MacKay, R. S.

2018-02-01

Complex dynamical systems are systems with many interdependent components which evolve in time. One might wish to control their trajectories, but a more practical alternative is to control just their statistical behaviour. In many contexts this would be both sufficient and a more realistic goal, e.g. climate and socio-economic systems. I refer to it as ‘management’ of complex dynamical systems. In this paper, some mathematics for management of complex dynamical systems is developed in the weakly dependent regime, and questions are posed for the strongly dependent regime.

Supporting complex search tasks

DEFF Research Database (Denmark)

Gäde, Maria; Hall, Mark; Huurdeman, Hugo

2015-01-01

, is fragmented at best. The workshop addressed the many open research questions: What are the obvious use cases and applications of complex search? What are essential features of work tasks and search tasks to take into account? And how do these evolve over time? With a multitude of information, varying from...

76 FR 14678 - Communications Unit Leader Prerequisite and Evaluation

Science.gov (United States)

2011-03-17

... evaluation form. OEC will use the evaluation form to identify course attendees, verify satisfaction of course... and evaluation of OEC events. Evaluation forms will be available in hard copy at each training session... Prerequisite and Evaluation. OMB Number: 1670--NEW. COML Prerequisites Verification Frequency: On occasion...

The influence of ascorbic acid on the oxygen consumption and the heat production by the cells of wheat seedling roots with their mitochondrial electron transport chain inhibited at complexes I and III

International Nuclear Information System (INIS)

Gordon, L.K.; Rakhmatullina, D.F.; Ogorodnikova, T.I.; Alyabyev, A.J.; Minibayeva, F.V.; Loseva, N.L.; Mityashina, S.Y.

2007-01-01

The influence of exogenous ascorbic acid (AsA) on oxidative phosphorylation was studied using wheat seedling roots. Treatment of them with AsA stimulated the rates of oxygen consumption and the heat production and caused a decrease of the respiratory coefficient. The increase in respiration was prevented by inhibitors of ascorbate oxidase, diethyldithiocarbamate (DEDTC), and of cytochrome oxidase, cyanide (KCN). Exogenous AsA sharply stimulated the rate of oxygen consumption of roots when complexes I and III of the mitochondrial electron transport chain were inhibited by rotenone and antimycin A, respectively, while the rates of heat production did not change significantly. It is concluded that AsA is a potent energy substrate, which can be used in conditions of failing I and III complexes in the mitochondrial electron transport chain

Endophytic infection alleviates Pb{sup 2+} stress effects on photosystem II functioning of Oryza sativa leaves

Energy Technology Data Exchange (ETDEWEB)

Li, Xuemei, E-mail: lxmls132@163.com [College of Chemistry and Life Science, Shenyang Normal University, Shenyang 110034 (China); Zhang, Lihong, E-mail: lihongzhang132@163.com [Environmental Science Department of Liaoning University,Shenyang 110036 (China)

2015-09-15

Highlights: • Chl fluorescence parameters of endophyte-infected rice under Pb{sup 2+} stress were tested. • The efficiency and stability of PSII are markedly affected by Pb{sup 2+} stress. • Endophyte infection improved photosynthetic system activity under Pb{sup 2+} stress. • JIP-test is a suitable tool for monitoring of Pb{sup 2+} stress. • Endophyte infection may increase tolerance to Pb{sup 2+} in rice. - Abstract: The aims of this study were to examine the effect of Pb{sup 2+} stress on the primary reaction of photosynthesis and to assess the potential benefits of endophytic infection on the Pb{sup 2+} tolerance of rice seedlings. Rice inoculated with an endophytic fungus (E+) and non-inoculated (E−) were subjected to 0, 50, 100, 150 and 200 μM Pb{sup 2+}. The responses to Pb{sup 2+} stress were characterized by the analysis of Chl a fluorescence. A comparison of E− with E+ rice seedlings, as evaluated by their performance index (PI{sub ABS} and PI{sub tot}), revealed the inhibitory effects of Pb{sup 2+} on photosystem II (PSII) connectivity, the oxygen evolving complex (OEC), and on the J step of the induction curves, which is associated with an inhibition of electron transport from the quinone acceptor Q{sub A} to Q{sub B}. Furthermore, the changes of the donor and the acceptor parameters of PSII were greater in E− than in E+ under Pb{sup 2+} stress. These observations suggest that the efficiency and stability of PSII are markedly affected by Pb{sup 2+} stress, and the photosynthetic energy conservation in E+ was more effective than in E−. We showed that endophytic infection plays an important role in enhancing the photosynthetic mechanism of rice seedlings exposed to Pb{sup 2+} stress.

On Measuring the Complexity of Networks: Kolmogorov Complexity versus Entropy

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Mikołaj Morzy

2017-01-01

Full Text Available One of the most popular methods of estimating the complexity of networks is to measure the entropy of network invariants, such as adjacency matrices or degree sequences. Unfortunately, entropy and all entropy-based information-theoretic measures have several vulnerabilities. These measures neither are independent of a particular representation of the network nor can capture the properties of the generative process, which produces the network. Instead, we advocate the use of the algorithmic entropy as the basis for complexity definition for networks. Algorithmic entropy (also known as Kolmogorov complexity or K-complexity for short evaluates the complexity of the description required for a lossless recreation of the network. This measure is not affected by a particular choice of network features and it does not depend on the method of network representation. We perform experiments on Shannon entropy and K-complexity for gradually evolving networks. The results of these experiments point to K-complexity as the more robust and reliable measure of network complexity. The original contribution of the paper includes the introduction of several new entropy-deceiving networks and the empirical comparison of entropy and K-complexity as fundamental quantities for constructing complexity measures for networks.

A fusion of minicircle DNA and nanoparticle delivery technologies facilitates therapeutic genetic engineering of autologous canine olfactory mucosal cells.

Science.gov (United States)

Delaney, Alexander M; Adams, Christopher F; Fernandes, Alinda R; Al-Shakli, Arwa F; Sen, Jon; Carwardine, Darren R; Granger, Nicolas; Chari, Divya M

2017-06-29

Olfactory ensheathing cells (OECs) promote axonal regeneration and improve locomotor function when transplanted into the injured spinal cord. A recent clinical trial demonstrated improved motor function in domestic dogs with spinal injury following autologous OEC transplantation. Their utility in canines offers promise for human translation, as dogs are comparable to humans in terms of clinical management and genetic/environmental variation. Moreover, the autologous, minimally invasive derivation of OECs makes them viable for human spinal injury investigation. Genetic engineering of transplant populations may augment their therapeutic potential, but relies heavily on viral methods which have several drawbacks for clinical translation. We present here the first proof that magnetic particles deployed with applied magnetic fields and advanced DNA minicircle vectors can safely bioengineer OECs to secrete a key neurotrophic factor, with an efficiency approaching that of viral vectors. We suggest that our alternative approach offers high translational potential for the delivery of augmented clinical cell therapies.

Carotenoids, versatile components of oxygenic photosynthesis.

Science.gov (United States)

Domonkos, Ildikó; Kis, Mihály; Gombos, Zoltán; Ughy, Bettina

2013-10-01

Carotenoids (CARs) are a group of pigments that perform several important physiological functions in all kingdoms of living organisms. CARs serve as protective agents, which are essential structural components of photosynthetic complexes and membranes, and they play an important role in the light harvesting mechanism of photosynthesizing plants and cyanobacteria. The protection against reactive oxygen species, realized by quenching of singlet oxygen and the excited states of photosensitizing molecules, as well as by the scavenging of free radicals, is one of the main biological functions of CARs. X-ray crystallographic localization of CARs revealed that they are present at functionally and structurally important sites of both the PSI and PSII reaction centers. Characterization of a CAR-less cyanobacterial mutant revealed that while the absence of CARs prevents the formation of PSII complexes, it does not abolish the assembly and function of PSI. CAR molecules assist in the formation of protein subunits of the photosynthetic complexes by gluing together their protein components. In addition to their aforementioned indispensable functions, CARs have a substantial role in the formation and maintenance of proper cellular architecture, and potentially also in the protection of the translational machinery under stress conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Structural insights into the metabolism of 2-chlorodibenzofuran by an evolved biphenyl dioxygenase

Energy Technology Data Exchange (ETDEWEB)

Kumar, Pravindra; Mohammadi, Mahmood; Dhindwal, Sonali; Pham, Thi Thanh My; Bolin, Jeffrey T.; Sylvestre, Michel (INRS); (IIT-India); (Purdue)

2012-06-28

The biphenyl dioxygenase of Burkholderia xenovorans LB400 (BphAE{sub LB400}) is a Rieske-type oxygenase that catalyzes the stereospecific oxygenation of many heterocyclic aromatics including dibenzofuran. In a previous work, we evolved BphAE{sub LB400} and obtained BphAE{sub RR41}. This variant metabolizes dibenzofuran and 2-chlorodibenzofuran more efficiently than BphAE{sub LB400}. However, the regiospecificity of BphAE{sub RR41} toward these substrates differs. Dibenzofuran is metabolized principally through a lateral dioxygenation whereas 2-chlorodibenzofuran is metabolized principally through an angular dioxygenation. In order to explain this difference, we examined the crystal structures of both substrate-bound forms of BphAE{sub RR41} obtained under anaerobic conditions. This structure analysis, in combination with biochemical data for a Ser283Gly mutant provided evidences that the substrate is compelled to move after oxygen-binding in BphAE{sub RR41}:dibenzofuran. In BphAE{sub RR41}:2-chlorodibenzofuran, the chlorine atom is close to the side chain of Ser283. This contact is missing in the BphAE{sub RR41}:dibenzofuran, and strong enough in the BphAE{sub RR41}:2-chlorodibenzofuran to help prevent substrate movement during the catalytic reaction.

Network Analysis of Earth's Co-Evolving Geosphere and Biosphere

Science.gov (United States)

Hazen, R. M.; Eleish, A.; Liu, C.; Morrison, S. M.; Meyer, M.; Consortium, K. D.

2017-12-01

A fundamental goal of Earth science is the deep understanding of Earth's dynamic, co-evolving geosphere and biosphere through deep time. Network analysis of geo- and bio- `big data' provides an interactive, quantitative, and predictive visualization framework to explore complex and otherwise hidden high-dimension features of diversity, distribution, and change in the evolution of Earth's geochemistry, mineralogy, paleobiology, and biochemistry [1]. Networks also facilitate quantitative comparison of different geological time periods, tectonic settings, and geographical regions, as well as different planets and moons, through network metrics, including density, centralization, diameter, and transitivity.We render networks by employing data related to geographical, paragenetic, environmental, or structural relationships among minerals, fossils, proteins, and microbial taxa. An important recent finding is that the topography of many networks reflects parameters not explicitly incorporated in constructing the network. For example, networks for minerals, fossils, and protein structures reveal embedded qualitative time axes, with additional network geometries possibly related to extinction and/or other punctuation events (see Figure). Other axes related to chemical activities and volatile fugacities, as well as pressure and/or depth of formation, may also emerge from network analysis. These patterns provide new insights into the way planets evolve, especially Earth's co-evolving geosphere and biosphere. 1. Morrison, S.M. et al. (2017) Network analysis of mineralogical systems. American Mineralogist 102, in press. Figure Caption: A network of Phanerozoic Era fossil animals from the past 540 million years includes blue, red, and black circles (nodes) representing family-level taxa and grey lines (links) between coexisting families. Age information was not used in the construction of this network; nevertheless an intrinsic timeline is embedded in the network topology. In

Evolution and the complexity of bacteriophages.

Science.gov (United States)

Serwer, Philip

2007-03-13

The genomes of both long-genome (> 200 Kb) bacteriophages and long-genome eukaryotic viruses have cellular gene homologs whose selective advantage is not explained. These homologs add genomic and possibly biochemical complexity. Understanding their significance requires a definition of complexity that is more biochemically oriented than past empirically based definitions. Initially, I propose two biochemistry-oriented definitions of complexity: either decreased randomness or increased encoded information that does not serve immediate needs. Then, I make the assumption that these two definitions are equivalent. This assumption and recent data lead to the following four-part hypothesis that explains the presence of cellular gene homologs in long bacteriophage genomes and also provides a pathway for complexity increases in prokaryotic cells: (1) Prokaryotes underwent evolutionary increases in biochemical complexity after the eukaryote/prokaryote splits. (2) Some of the complexity increases occurred via multi-step, weak selection that was both protected from strong selection and accelerated by embedding evolving cellular genes in the genomes of bacteriophages and, presumably, also archaeal viruses (first tier selection). (3) The mechanisms for retaining cellular genes in viral genomes evolved under additional, longer-term selection that was stronger (second tier selection). (4) The second tier selection was based on increased access by prokaryotic cells to improved biochemical systems. This access was achieved when DNA transfer moved to prokaryotic cells both the more evolved genes and their more competitive and complex biochemical systems. I propose testing this hypothesis by controlled evolution in microbial communities to (1) determine the effects of deleting individual cellular gene homologs on the growth and evolution of long genome bacteriophages and hosts, (2) find the environmental conditions that select for the presence of cellular gene homologs, (3) determine

Evolution and the complexity of bacteriophages

Directory of Open Access Journals (Sweden)

Serwer Philip

2007-03-01

Full Text Available Abstract Background The genomes of both long-genome (> 200 Kb bacteriophages and long-genome eukaryotic viruses have cellular gene homologs whose selective advantage is not explained. These homologs add genomic and possibly biochemical complexity. Understanding their significance requires a definition of complexity that is more biochemically oriented than past empirically based definitions. Hypothesis Initially, I propose two biochemistry-oriented definitions of complexity: either decreased randomness or increased encoded information that does not serve immediate needs. Then, I make the assumption that these two definitions are equivalent. This assumption and recent data lead to the following four-part hypothesis that explains the presence of cellular gene homologs in long bacteriophage genomes and also provides a pathway for complexity increases in prokaryotic cells: (1 Prokaryotes underwent evolutionary increases in biochemical complexity after the eukaryote/prokaryote splits. (2 Some of the complexity increases occurred via multi-step, weak selection that was both protected from strong selection and accelerated by embedding evolving cellular genes in the genomes of bacteriophages and, presumably, also archaeal viruses (first tier selection. (3 The mechanisms for retaining cellular genes in viral genomes evolved under additional, longer-term selection that was stronger (second tier selection. (4 The second tier selection was based on increased access by prokaryotic cells to improved biochemical systems. This access was achieved when DNA transfer moved to prokaryotic cells both the more evolved genes and their more competitive and complex biochemical systems. Testing the hypothesis I propose testing this hypothesis by controlled evolution in microbial communities to (1 determine the effects of deleting individual cellular gene homologs on the growth and evolution of long genome bacteriophages and hosts, (2 find the environmental conditions that

Magnetic field protects plants against high light by slowing down production of singlet oxygen

Czech Academy of Sciences Publication Activity Database

Hakala-Yatkin, M.; Sarvikas, P.; Paturi, P.; Mattila, H.; Tyystjärvi, T.; Nedbal, Ladislav; Tyystjärvi, E.

2011-01-01

Roč. 142, č. 1 (2011), s. 26-34 ISSN 0031-9317 Institutional research plan: CEZ:AV0Z60870520 Keywords : photosynthetic reaction-center * Photosystem-II * alpha-tocopherol * environmental-stress * manganese complex * evolving complex * oxidative stress Subject RIV: EH - Ecology, Behaviour Impact factor: 3.112, year: 2011

The Complex Relationship of Extracorporeal Membrane Oxygenation and Acute Kidney Injury: Causation or Association?

Science.gov (United States)

Kilburn, Daniel J; Shekar, Kiran; Fraser, John F

2016-01-01

Extracorporeal membrane oxygenation (ECMO) is a modified cardiopulmonary bypass (CPB) circuit capable of providing prolonged cardiorespiratory support. Recent advancement in ECMO technology has resulted in increased utilisation and clinical application. It can be used as a bridge-to-recovery, bridge-to-bridge, bridge-to-transplant, or bridge-to-decision. ECMO can restitute physiology in critically ill patients, which may minimise the risk of progressive multiorgan dysfunction. Alternatively, iatrogenic complications of ECMO clearly contribute to worse outcomes. These factors affect the risk : benefit ratio of ECMO which ultimately influence commencement/timing of ECMO. The complex interplay of pre-ECMO, ECMO, and post-ECMO pathophysiological processes are responsible for the substantial increased incidence of ECMO-associated acute kidney injury (EAKI). The development of EAKI significantly contributes to morbidity and mortality; however, there is a lack of evidence defining a potential benefit or causative link between ECMO and AKI. This area warrants investigation as further research will delineate the mechanisms involved and subsequent strategies to minimise the risk of EAKI. This review summarizes the current literature of ECMO and AKI, considers the possible benefits and risks of ECMO on renal function, outlines the related pathophysiology, highlights relevant investigative tools, and ultimately suggests an approach for future research into this under investigated area of critical care.

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Perched Water Samples

Energy Technology Data Exchange (ETDEWEB)

Lee, Brady D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moran, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nims, Megan K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Saunders, Danielle L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2017-04-13

Fine-grained sediments associated with the Cold Creek Unit at Hanford have caused the formation of a perched water aquifer in the deep vadose zone at the B Complex area, which includes waste sites in the 200-DV-1 Operable Unit and the single-shell tank farms in Waste Management Area B-BX-BY. High levels of contaminants, such as uranium, technetium-99, and nitrate, make this aquifer a continuing source of contamination for the groundwater located a few meters below the perched zone. Analysis of deuterium (²H) and 18-oxygen (¹⁸O) of nine perched water samples from three different wells was performed. Samples represent time points from hydraulic tests performed on the perched aquifer using the three wells. The isotope analyses showed that the perched water had δ²H and δ¹⁸O ratios consistent with the regional meteoric water line, indicating that local precipitation events at the Hanford site likely account for recharge of the perched water aquifer. Data from the isotope analysis can be used along with pumping and recovery data to help understand the perched water dynamics related to aquifer size and hydraulic control of the aquifer in the future.

On the Benefits of Divergent Search for Evolved Representations

DEFF Research Database (Denmark)

Lehman, Joel; Risi, Sebastian; Stanley, Kenneth O

2012-01-01

Evolved representations in evolutionary computation are often fragile, which can impede representation-dependent mechanisms such as self-adaptation. In contrast, evolved representations in nature are robust, evolvable, and creatively exploit available representational features. This paper provide...

Polarized X-ray absorption spectroscopy of single-crystal Mn(V) complexes relevant to the oxygen-evolving complex of photosystem II

DEFF Research Database (Denmark)

Yano, Junko; Robblee, John; Pushkar, Yulia

2007-01-01

High-valent Mn-oxo species have been suggested to have a catalytically important role in the water splitting reaction which occurs in the Photosystem II membrane protein. In this study, five- and six-coordinate mononuclear Mn(V) compounds were investigated by polarized X-ray absorption spectroscopy...... structure of the metal site was then studied by measuring the polarization dependence of X-ray absorption near-edge spectroscopy (XANES) pre-edge spectra (1s to 3d transition) and comparing with the results of density functional theory (DFT) calculations. The Mn(V)-nitrido compound, in which the manganese......-edge peak. This component was interpreted as a 1s to 3d(xz,yz) transition with 4px,y mixing, due to the displacement of the Mn atom out of the equatorial plane. The XANES results have been correlated to DFT calculations, and the spectra have been simulated using a TD (time-dependent)-DFT approach...

Making Communication Strategy Choices in a Fast Evolving Crisis Situation—Results from a Table-Top Discussion on an Anthrax Scenario

Directory of Open Access Journals (Sweden)

Aino Ruggiero

2016-05-01

Full Text Available This paper aims at clarifying a timely topic of how communication strategy choices are made in evolving, complex crises, such as those caused by terrorism involving chemical, biological, radiological, or nuclear (CBRN agents. This is done by examining data gathered from a table-top discussion among crisis communication experts, focusing on a scenario of an anthrax attack and analysed qualitatively. The communication experts followed the evolving crisis situation by gathering inputs from various actors in the crisis management network, thereby creating situational understanding, and interpreted these inputs for decision-making on communication strategies. The underlying process of coping with complexity in evolving CBRN terrorism crises can be described as a continuous, dynamic process that can best be explained with a combination of traditional and more modern crisis communication approaches. Strategy-making in crisis situations by communication experts is still largely a black box. In this study, a novel approach of decomposing strategy-making by observing a table-top discussion is chosen to clarify the process. By identifying the core elements involved, a more detailed picture of communication strategy-making is created, thus promoting preparedness and professional resilience in the field.

Effect of high hydrostatic pressure on small oxygen-related clusters in silicon: LVM studies

International Nuclear Information System (INIS)

Murin, L.I.; Lindstroem, J.L.; Misiuk, A.

2003-01-01

Local vibrational mode (LVM) spectroscopy is used to explore the effect of high hydrostatic pressure (HP) on the formation of small oxygen-related clusters (dimers, trimers, thermal donors, and C-O complexes) at 450 deg. C and 650 deg. C in Cz-Si crystals with different impurity content and prehistory. It is found, in agreement with previous studies, that HP enhances the oxygen clustering in Cz-Si at elevated temperatures. The effect of HP is related mainly to enhancement in the diffusivity of single oxygen atoms and small oxygen aggregates. HP does not noticeably increase the binding energies of the most simple oxygen related complexes like O 2i , C s O ni . The biggest HP effect on the thermal double donor (TDDs) generation is revealed in hydrogenated samples. Heat-treatment of such samples at 450 deg. C under HP results in extremely high TDD introduction rates as well as in a strong increase in the concentration of the first TDD species

Anatomical Network Analysis Shows Decoupling of Modular Lability and Complexity in the Evolution of the Primate Skull

Science.gov (United States)

Esteve-Altava, Borja; Boughner, Julia C.; Diogo, Rui; Villmoare, Brian A.; Rasskin-Gutman, Diego

2015-01-01

Modularity and complexity go hand in hand in the evolution of the skull of primates. Because analyses of these two parameters often use different approaches, we do not know yet how modularity evolves within, or as a consequence of, an also-evolving complex organization. Here we use a novel network theory-based approach (Anatomical Network Analysis) to assess how the organization of skull bones constrains the co-evolution of modularity and complexity among primates. We used the pattern of bone contacts modeled as networks to identify connectivity modules and quantify morphological complexity. We analyzed whether modularity and complexity evolved coordinately in the skull of primates. Specifically, we tested Herbert Simon’s general theory of near-decomposability, which states that modularity promotes the evolution of complexity. We found that the skulls of extant primates divide into one conserved cranial module and up to three labile facial modules, whose composition varies among primates. Despite changes in modularity, statistical analyses reject a positive feedback between modularity and complexity. Our results suggest a decoupling of complexity and modularity that translates to varying levels of constraint on the morphological evolvability of the primate skull. This study has methodological and conceptual implications for grasping the constraints that underlie the developmental and functional integration of the skull of humans and other primates. PMID:25992690

Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

Energy Technology Data Exchange (ETDEWEB)

Szamocki, R.; Flexer, V. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Levin, L.; Forchiasin, F. [Micologia Experimental, Departamento de Biodiversidad y Biologia Experimental. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Calvo, E.J. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina)], E-mail: calvo@qi.fcen.uba.ar

2009-02-28

Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated.

Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

International Nuclear Information System (INIS)

Szamocki, R.; Flexer, V.; Levin, L.; Forchiasin, F.; Calvo, E.J.

2009-01-01

Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated

The genotype-phenotype map of an evolving digital organism

OpenAIRE

Fortuna, Miguel A.; Zaman, Luis; Ofria, Charles; Wagner, Andreas

2017-01-01

To understand how evolving systems bring forth novel and useful phenotypes, it is essential to understand the relationship between genotypic and phenotypic change. Artificial evolving systems can help us understand whether the genotype-phenotype maps of natural evolving systems are highly unusual, and it may help create evolvable artificial systems. Here we characterize the genotype-phenotype map of digital organisms in Avida, a platform for digital evolution. We consider digital organisms fr...

Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.

Science.gov (United States)

Mitra, Mainak; Nimir, Hassan; Demeshko, Serhiy; Bhat, Satish S; Malinkin, Sergey O; Haukka, Matti; Lloret-Fillol, Julio; Lisensky, George C; Meyer, Franc; Shteinman, Albert A; Browne, Wesley R; Hrovat, David A; Richmond, Michael G; Costas, Miquel; Nordlander, Ebbe

2015-08-03

Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L(2)), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [Fe(II)(CH3CN)(L)](2+) (L = L(1) (1); L(2) (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [Fe(IV)(O)(L)](2+) (L = L(1) (3); L(2) (4)), which were characterized by UV-vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L(1)) and 2.5 h (L = L(2)). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([Fe(IV)(O)(N4Py)](2+)), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [Fe(IV)(O)(L(2))](2+) exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C-H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.

Myoglobin oxygen affinity in aquatic and terrestrial birds and mammals.

Science.gov (United States)

Wright, Traver J; Davis, Randall W

2015-07-01

Myoglobin (Mb) is an oxygen binding protein found in vertebrate skeletal muscle, where it facilitates intracellular transport and storage of oxygen. This protein has evolved to suit unique physiological needs in the muscle of diving vertebrates that express Mb at much greater concentrations than their terrestrial counterparts. In this study, we characterized Mb oxygen affinity (P50) from 25 species of aquatic and terrestrial birds and mammals. Among diving species, we tested for correlations between Mb P50 and routine dive duration. Across all species examined, Mb P50 ranged from 2.40 to 4.85 mmHg. The mean P50 of Mb from terrestrial ungulates was 3.72±0.15 mmHg (range 3.70-3.74 mmHg). The P50 of cetaceans was similar to terrestrial ungulates ranging from 3.54 to 3.82 mmHg, with the exception of the melon-headed whale, which had a significantly higher P50 of 4.85 mmHg. Among pinnipeds, the P50 ranged from 3.23 to 3.81 mmHg and showed a trend for higher oxygen affinity in species with longer dive durations. Among diving birds, the P50 ranged from 2.40 to 3.36 mmHg and also showed a trend of higher affinities in species with longer dive durations. In pinnipeds and birds, low Mb P50 was associated with species whose muscles are metabolically active under hypoxic conditions associated with aerobic dives. Given the broad range of potential globin oxygen affinities, Mb P50 from diverse vertebrate species appears constrained within a relatively narrow range. High Mb oxygen affinity within this range may be adaptive for some vertebrates that make prolonged dives. © 2015. Published by The Company of Biologists Ltd.

75 FR 5608 - National Protection and Programs Directorate; Communications Unit Leader (COML) Prerequisite and...

Science.gov (United States)

2010-02-03

... assurance and improvement purposes, evaluation data will be collected in an evaluation form. OEC will use... electronic but can also be received in paper form to facilitate ease of registration and evaluation of OEC events. Evaluation forms will be available in hard copy at each training session, and time will be...

Oxygen Transport Membranes

Energy Technology Data Exchange (ETDEWEB)

S. Bandopadhyay

2008-08-30

small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume

Revisiting Robustness and Evolvability: Evolution in Weighted Genotype Spaces

Science.gov (United States)

Partha, Raghavendran; Raman, Karthik

2014-01-01

Robustness and evolvability are highly intertwined properties of biological systems. The relationship between these properties determines how biological systems are able to withstand mutations and show variation in response to them. Computational studies have explored the relationship between these two properties using neutral networks of RNA sequences (genotype) and their secondary structures (phenotype) as a model system. However, these studies have assumed every mutation to a sequence to be equally likely; the differences in the likelihood of the occurrence of various mutations, and the consequence of probabilistic nature of the mutations in such a system have previously been ignored. Associating probabilities to mutations essentially results in the weighting of genotype space. We here perform a comparative analysis of weighted and unweighted neutral networks of RNA sequences, and subsequently explore the relationship between robustness and evolvability. We show that assuming an equal likelihood for all mutations (as in an unweighted network), underestimates robustness and overestimates evolvability of a system. In spite of discarding this assumption, we observe that a negative correlation between sequence (genotype) robustness and sequence evolvability persists, and also that structure (phenotype) robustness promotes structure evolvability, as observed in earlier studies using unweighted networks. We also study the effects of base composition bias on robustness and evolvability. Particularly, we explore the association between robustness and evolvability in a sequence space that is AU-rich – sequences with an AU content of 80% or higher, compared to a normal (unbiased) sequence space. We find that evolvability of both sequences and structures in an AU-rich space is lesser compared to the normal space, and robustness higher. We also observe that AU-rich populations evolving on neutral networks of phenotypes, can access less phenotypic variation compared to

Impact of the spatial distribution of morphological pattern on the efficiency of electrocatalytic gas evolving reactions

Directory of Open Access Journals (Sweden)

Žerađanin Aleksandar R.

2014-01-01

Full Text Available The efficiency of electrocatalytic gas evolving reactions (hydrogen, chlorine and oxygen evolution is a key challenge for the important industrial processes, such as chlor-alkali electrolysis or water electrolysis. Central issue for the aforementioned electrocatalytic processes is huge power consumption. Experimental results accumulated in the past, as well as some predictive models ("volcano" plots indicate that altering the nature of the electrode material cannot significantly increase the activity of mentioned reactions. Consequently, it is necessary to find a qualitatively different strategy for improving the energy efficiency of electrocatalytic gas evolving reactions. Usually disregarded fact is that the gas evolution is an oscillatory phenomenon. Given the oscillatory behavior, a key parameter of macrokinetics of gas electrode is the frequency of gas-bubble detachment. Bearing in mind that the gas evolution greatly depends on the surface morphology, a methodology is proposed that establishes a rational link between the morphological pattern of electrode with electrode activity and stability. Characterization was performed using advanced analytical tools. Frequency of gas-bubble detachment is obtained in the configuration of scanning electrochemical microscopy (SECM while the corrosion stability is analyzed using miniaturized scanning flow electrochemical cell connected to the mass spectrometer (SFC-ICPMS.

A diamine ligand with long 'arms' and its corresponding dinuclear rhenium(I) complex: Synthesis, characterization, photophysical property, and sensing activity towards molecular oxygen

Energy Technology Data Exchange (ETDEWEB)

Xu Xiaoyong, E-mail: dreamxxy01@163.com [Center for Functional Materials of Pingxiang, Pingxiang 337055 (China) and College of Materials Science and Engineering, Hunan University, Changsha 410082 (China); Xiao Hanning [College of Materials Science and Engineering, Hunan University, Changsha 410082 (China)

2012-09-15

In this paper, we synthesize a novel diamine ligand of 4,7-dinonadecyl-1,10-phenanthroline (DN-Phen) with two long alkyl chain arms serving as a shield and its corresponding dinuclear Re(I) complex of Re{sub 2}(CO){sub 6}(bpy)(DN-Phen){sub 2} (bpy=4,4 Prime -bipyridine), aiming at an optical sensor immune to the surrounding interferences. Its geometric and electronic structures are investigated, which suggest that the introduced long alkyl chains act as a shield for the excited state of emissive center. The promising photophysical parameters of Re{sub 2}(CO){sub 6}(bpy)(DN-Phen){sub 2}, including the immunity of emission towards the surrounding interferences and long excited state lifetime, make itself a potential probe for oxygen detection. By doping Re{sub 2}(CO){sub 6}(bpy)(DN-Phen){sub 2} into two silica matrixes of MCM-41 and SBA-15, oxygen sensing performances of the resulted composite materials are investigated. Finally, a high sensitivity of 20.1 is realized, with short response/recovery time of 8 s/42 s. Here, sensitivity is defined as the ratio of emission maximum under pure nitrogen to emission minimum under pure oxygen, response and recovery times are the times for a sample to lose (response time) or recover (recovery time) 95% of its emission maximum upon periodically changed atmosphere. - Highlights: Black-Right-Pointing-Pointer A ligand with two long alkyl chain arms serving as a shield is synthesized. Black-Right-Pointing-Pointer The shield protects the excited state emissive center. Black-Right-Pointing-Pointer The emission of Re(I) complex is immune towards surrounding interference. Black-Right-Pointing-Pointer A high sensitivity of 20.1 is realized.

Investigation of Plasmas Having Complex, Dynamic Evolving Morphology

Energy Technology Data Exchange (ETDEWEB)

Bellan, Paul M. [California Inst. of Technology (CalTech), Pasadena, CA (United States)

2017-01-03

Three different types of plasmas have been investigated using both experimental and theoretical methods. The first type of plasma is dense, highly ionized, governed by magnetohydrodynamics, and highly dynamic. This plasma is relevant to solar coronal loops, astrophysical jets, and other situations where strong magnetic forces act on the plasma. A well-diagnosed laboratory experiment creates a magnetohydrodynamically driven highly collimated plasma jet. This jet undergoes a kink instability such that it rapidly develops a corkscrew shape. The kink causes lateral acceleration of the jet, and this lateral acceleration drives a Rayleigh-Taylor instability that in turn chokes the current flowing in the jet and causes a magnetic reconnection. The magnetic reconnection causes electron and ion heating as well as emission of whistler waves. This entire sequence of events has been observed, measured in detail, and related to theoretical models. The second type of plasma is a transient rf-produced plasma used as a seed plasma for the magnetohydrodynamic experiments described above. Detailed atomic physics ionization processes have been investigated and modeled. The third type of plasma that has been studied is a dusty plasma where the dust particles are spontaneously growing ice grains. The rapid growth of the ice grains to large size and their highly ordered alignment has been investigated as well as collective motion of the ice grains, including well-defined flows on the surface of nested toroids. In addition to the experimental work described above, several related theoretical models have been developed, most notably a model showing how a complex interaction between gravity and magnetic fields on extremely weakly ionized plasma in an accretion disk provides an electric power source that can drive astrophysical jets associated with the accretion disk. Eighteen papers reporting this work have been published in a wide variety of journals.

Investigation of Plasmas Having Complex, Dynamic Evolving Morphology

International Nuclear Information System (INIS)

Bellan, Paul M.

2017-01-01

Three different types of plasmas have been investigated using both experimental and theoretical methods. The first type of plasma is dense, highly ionized, governed by magnetohydrodynamics, and highly dynamic. This plasma is relevant to solar coronal loops, astrophysical jets, and other situations where strong magnetic forces act on the plasma. A well-diagnosed laboratory experiment creates a magnetohydrodynamically driven highly collimated plasma jet. This jet undergoes a kink instability such that it rapidly develops a corkscrew shape. The kink causes lateral acceleration of the jet, and this lateral acceleration drives a Rayleigh-Taylor instability that in turn chokes the current flowing in the jet and causes a magnetic reconnection. The magnetic reconnection causes electron and ion heating as well as emission of whistler waves. This entire sequence of events has been observed, measured in detail, and related to theoretical models. The second type of plasma is a transient rf-produced plasma used as a seed plasma for the magnetohydrodynamic experiments described above. Detailed atomic physics ionization processes have been investigated and modeled. The third type of plasma that has been studied is a dusty plasma where the dust particles are spontaneously growing ice grains. The rapid growth of the ice grains to large size and their highly ordered alignment has been investigated as well as collective motion of the ice grains, including well-defined flows on the surface of nested toroids. In addition to the experimental work described above, several related theoretical models have been developed, most notably a model showing how a complex interaction between gravity and magnetic fields on extremely weakly ionized plasma in an accretion disk provides an electric power source that can drive astrophysical jets associated with the accretion disk. Eighteen papers reporting this work have been published in a wide variety of journals.

Singlet oxygen quenching by oxygen in tetraphenyl-porphyrin solutions

International Nuclear Information System (INIS)

Dedic, Roman; Korinek, Miloslav; Molnar, Alexander; Svoboda, Antonin; Hala, Jan

2006-01-01

Time-resolved measurement of singlet oxygen infrared phosphorescence is a powerful tool for determination of quantum yields and kinetics of its photosensitization. This technique was employed to investigate in detail the previously observed effect of singlet oxygen quenching by oxygen. The question whether the singlet oxygen is quenched by oxygen in ground or in excited state was addressed by study of two complementary dependencies of singlet oxygen lifetimes: on dissolved oxygen concentration and on excitation intensity. Oxygen concentration dependence study of meso-tetra(4-sulphonato)phenylporphyrin (TPPS 4 ) phosphorescence kinetics showed linearity of the dependence of TPPS 4 triplet state rate-constant. Corresponding bimolecular quenching constant of (1.5±0.1)x10 9 l/mol s was obtained. On the other hand, rate constants of singlet oxygen depopulation exhibit nonlinear dependence on oxygen concentration. Comparison of zero oxygen concentration-extrapolated value of singlet oxygen lifetime of (6.5±0.4) μs to (3.7±0.1) μs observed under air-saturated conditions indicates importance of the effect of quenching of singlet oxygen by oxygen. Upward-sloping dependencies of singlet oxygen depopulation rate-constant on excitation intensity evidence that singlet oxygen is predominantly quenched by oxygen in excited singlet state

Use of the parameterised finite element method to robustly and efficiently evolve the edge of a moving cell.

Science.gov (United States)

Neilson, Matthew P; Mackenzie, John A; Webb, Steven D; Insall, Robert H

2010-11-01

In this paper we present a computational tool that enables the simulation of mathematical models of cell migration and chemotaxis on an evolving cell membrane. Recent models require the numerical solution of systems of reaction-diffusion equations on the evolving cell membrane and then the solution state is used to drive the evolution of the cell edge. Previous work involved moving the cell edge using a level set method (LSM). However, the LSM is computationally very expensive, which severely limits the practical usefulness of the algorithm. To address this issue, we have employed the parameterised finite element method (PFEM) as an alternative method for evolving a cell boundary. We show that the PFEM is far more efficient and robust than the LSM. We therefore suggest that the PFEM potentially has an essential role to play in computational modelling efforts towards the understanding of many of the complex issues related to chemotaxis.

Leadership Behaviors of Management for Complex Adaptive Systems

Science.gov (United States)

2010-04-01

Leadership Behaviors of Management for Complex Adaptive Systems Systems and Software Technology Conference April 2010 Dr. Suzette S. Johnson...2010 2. REPORT TYPE 3. DATES COVERED 00-00-2010 to 00-00-2010 4. TITLE AND SUBTITLE Leadership Behaviors of Management for Complex Adaptive...as they evolve – Control is dispersed and decentralized – Simple rules and governance used to direct behavior • Complexity Leadership Theory – Built on

Characterizing 3-D flow velocity in evolving pore networks driven by CaCO3 precipitation and dissolution

Science.gov (United States)

Chojnicki, K. N.; Yoon, H.; Martinez, M. J.

2015-12-01

Understanding reactive flow in geomaterials is important for optimizing geologic carbon storage practices, such as using pore space efficiently. Flow paths can be complex in large degrees of geologic heterogeneities across scales. In addition, local heterogeneity can evolve as reactive transport processes alter the pore-scale morphology. For example, dissolved carbon dioxide may react with minerals in fractured rocks, confined aquifers, or faults, resulting in heterogeneous cementation (and/or dissolution) and evolving flow conditions. Both path and flow complexities are important and poorly characterized, making it difficult to determine their evolution with traditional 2-D transport models. Here we characterize the development of 3-D pore-scale flow with an evolving pore configuration due to calcium carbonate (CaCO3) precipitation and dissolution. A simple pattern of a microfluidic pore network is used initially and pore structures will become more complex due to precipitation and dissolution processes. At several stages of precipitation and dissolution, we directly visualize 3-D velocity vectors using micro particle image velocimetry and a laser scanning confocal microscope. Measured 3-D velocity vectors are then compared to 3-D simulated flow fields which will be used to simulate reactive transport. Our findings will highlight the importance of the 3-D flow dynamics and its impact on estimating reactive surface area over time. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This material is based upon work supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114.

Complex Adaptive Schools: Educational Leadership and School Change

Science.gov (United States)

Kershner, Brad; McQuillan, Patrick

2016-01-01

This paper utilizes the theoretical framework of complexity theory to compare and contrast leadership and educational change in two urban schools. Drawing on the notion of a complex adaptive system--an interdependent network of interacting elements that learns and evolves in adapting to an ever-shifting context--our case studies seek to reveal the…

Quadruple labelled dual oxygen and pH-sensitive ratiometric nanosensors

Directory of Open Access Journals (Sweden)

Veeren M. Chauhan

2016-05-01

Full Text Available Nanosensors capable of simultaneously measuring dissolved oxygen concentrations from 0 to 100% saturation and pH over the full physiological range, from pH 3.5 to 7.5, that advance the methods towards understanding of key biological gradients, were synthesised. A library of water soluble oxygen-sensitive porphyrins, with three substituted charged functional groups and a chemically flexible carboxylate functional group were spectroscopically analysed to assess their sensitivity to changes in dissolved oxygen concentrations as free species in solution and in suspension as nanoparticle conjugates. A platinum cationic porphyrin was taken forward to fabricate ratiometric oxygen-sensitive nanosensors, using 5-(and-6-carboxytetramethylrhodamine (TAMRA as internal standard. In addition, quadruple labelled dual oxygen and pH-sensitive nanosensors were synthesised using the cationic Pt porphyrin, pH-sensitive fluorescein dyes, carboxyfluorescein (FAM and Oregon Green (OG, in a 1:1 ratio, and TAMRA. We envisage the dual oxygen and pH nanosensors will find broad utility in the characterisation of diverse microenvironments, where there are complex interactions between molecular oxygen and pH. Keywords: Fluorescent, Phosphorescent, Nanosensor, Oxygen, pH, Ratiometric, Platinum metalloporphyrin

Tracking Oxygen Vacancies in Thin Film SOFC Cathodes

Science.gov (United States)

Leonard, Donovan; Kumar, Amit; Jesse, Stephen; Kalinin, Sergei; Shao-Horn, Yang; Crumlin, Ethan; Mutoro, Eva; Biegalski, Michael; Christen, Hans; Pennycook, Stephen; Borisevich, Albina

2011-03-01

Oxygen vacancies have been proposed to control the rate of the oxygen reduction reaction and ionic transport in complex oxides used as solid oxide fuel cell (SOFC) cathodes [1,2]. In this study oxygen vacancies were tracked, both dynamically and statically, with the combined use of scanned probe microscopy (SPM) and scanning transmission electron microscopy (STEM). Epitaxial films of La 0.8 Sr 0.2 Co O3 (L SC113) and L SC113 / LaSrCo O4 (L SC214) on a GDC/YSZ substrate were studied, where the latter showed increased electrocatalytic activity at moderate temperature. At atomic resolution, high angle annular dark field STEM micrographs revealed vacancy ordering in L SC113 as evidenced by lattice parameter modulation and EELS studies. The evolution of oxygen vacancy concentration and ordering with applied bias and the effects of bias cycling on the SOFC cathode performance will be discussed. Research is sponsored by the of Materials Sciences and Engineering Division, U.S. DOE.

Effect of micro-oxygenation and wood type on the phenolic composition and color of an aged red wine.

Science.gov (United States)

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.).

Adult venovenous extracorporeal membrane oxygenation for severe respiratory failure: Current status and future perspectives.

Science.gov (United States)

Sen, Ayan; Callisen, Hannelisa E; Alwardt, Cory M; Larson, Joel S; Lowell, Amelia A; Libricz, Stacy L; Tarwade, Pritee; Patel, Bhavesh M; Ramakrishna, Harish

2016-01-01

Extracorporeal membrane oxygenation (ECMO) for severe acute respiratory failure was proposed more than 40 years ago. Despite the publication of the ARDSNet study and adoption of lung protective ventilation, the mortality for acute respiratory failure due to acute respiratory distress syndrome has continued to remain high. This technology has evolved over the past couple of decades and has been noted to be safe and successful, especially during the worldwide H1N1 influenza pandemic with good survival rates. The primary indications for ECMO in acute respiratory failure include severe refractory hypoxemic and hypercarbic respiratory failure in spite of maximum lung protective ventilatory support. Various triage criteria have been described and published. Contraindications exist when application of ECMO may be futile or technically impossible. Knowledge and appreciation of the circuit, cannulae, and the physiology of gas exchange with ECMO are necessary to ensure lung rest, efficiency of oxygenation, and ventilation as well as troubleshooting problems. Anticoagulation is a major concern with ECMO, and the evidence is evolving with respect to diagnostic testing and use of anticoagulants. Clinical management of the patient includes comprehensive critical care addressing sedation and neurologic issues, ensuring lung recruitment, diuresis, early enteral nutrition, treatment and surveillance of infections, and multisystem organ support. Newer technology that delinks oxygenation and ventilation by extracorporeal carbon dioxide removal may lead to ultra-lung protective ventilation, avoidance of endotracheal intubation in some situations, and ambulatory therapies as a bridge to lung transplantation. Risks, complications, and long-term outcomes and resources need to be considered and weighed in before widespread application. Ethical challenges are a reality and a multidisciplinary approach that should be adopted for every case in consideration.

Characterization of chloroplast phosphoproteins controlling manganese use efficiency using quantitative proteomics

DEFF Research Database (Denmark)

Petersen, Jørgen; Sprenger, Richard Remko; Rogowska-Wrzesinska, Adelina

Manganese is important for molecular functions in plants, i.e. as a co-factor in enzymes and in the oxygen evolving complex of photosystem II, located like most of the photosynthetic machinery, in the thylakoid membranes of chloroplasts. Soils that lack plant available micronutrients such as mang......Manganese is important for molecular functions in plants, i.e. as a co-factor in enzymes and in the oxygen evolving complex of photosystem II, located like most of the photosynthetic machinery, in the thylakoid membranes of chloroplasts. Soils that lack plant available micronutrients...... involved in manganese use efficiency, focusing on the phosphoproteome from thylakoid preparations from two barley genotypes, manganese efficient (Vanessa) and inefficient (Antonia) genotype. Experimental: By monitoring the photosynthetic efficiency (Fv/Fm) a decline in activity is observed as a consequence...

Evolvability as a Quality Attribute of Software Architectures

NARCIS (Netherlands)

Ciraci, S.; van den Broek, P.M.; Duchien, Laurence; D'Hondt, Maja; Mens, Tom

We review the definition of evolvability as it appears on the literature. In particular, the concept of software evolvability is compared with other system quality attributes, such as adaptability, maintainability and modifiability.

Summary Report of Depleted Uranium (DU) Survey Actions at Nevada Test and Training Range (NTTR), Airspace Region 63B, Active Target Complex 10 (63-10)

Science.gov (United States)

2016-09-15

Sep 2016. a. In October 1992, the former Armstrong Laboratory Health Physics Function, now USAFSAM/OEC, took air and radiation samples during...in primary drainage areas, evidenced by the lack of DU activity above background in soil samples . However, survey measurements revealed elevated DU...and soil sampling in the primary drainage regions south of the active targets. It was also recommended that access to another area (NTTR 63-08

Iridium complexes for the application of photodynamic therapy

Directory of Open Access Journals (Sweden)

SHI Min

2015-10-01

Full Text Available Photodynamic therapy can destruct tumor cells by singlet oxygen which is generated via a photodynamic reaction of the photosensitizer under a specfic excitation wavelength.Due to the heavy atom effect of metal iridium,iridiumcomplexes are excited by suitable light and then reach their excited triple state through intersystem crossing.The excited iridium complexes transfer energy to oxygen molecules to produce singlet oxygen for photodynamic therapy.

The Complex Relationship of Extracorporeal Membrane Oxygenation and Acute Kidney Injury: Causation or Association?

Directory of Open Access Journals (Sweden)

Daniel J. Kilburn

2016-01-01

Full Text Available Extracorporeal membrane oxygenation (ECMO is a modified cardiopulmonary bypass (CPB circuit capable of providing prolonged cardiorespiratory support. Recent advancement in ECMO technology has resulted in increased utilisation and clinical application. It can be used as a bridge-to-recovery, bridge-to-bridge, bridge-to-transplant, or bridge-to-decision. ECMO can restitute physiology in critically ill patients, which may minimise the risk of progressive multiorgan dysfunction. Alternatively, iatrogenic complications of ECMO clearly contribute to worse outcomes. These factors affect the risk : benefit ratio of ECMO which ultimately influence commencement/timing of ECMO. The complex interplay of pre-ECMO, ECMO, and post-ECMO pathophysiological processes are responsible for the substantial increased incidence of ECMO-associated acute kidney injury (EAKI. The development of EAKI significantly contributes to morbidity and mortality; however, there is a lack of evidence defining a potential benefit or causative link between ECMO and AKI. This area warrants investigation as further research will delineate the mechanisms involved and subsequent strategies to minimise the risk of EAKI. This review summarizes the current literature of ECMO and AKI, considers the possible benefits and risks of ECMO on renal function, outlines the related pathophysiology, highlights relevant investigative tools, and ultimately suggests an approach for future research into this under investigated area of critical care.

Engineering the oxygen coordination in digital superlattices

Energy Technology Data Exchange (ETDEWEB)

Cook, Seyoung [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA; Department of Materials Science, Northwestern University, Evanston, Illinois 60202, USA; Andersen, Tassie K. [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA; Department of Materials Science, Northwestern University, Evanston, Illinois 60202, USA; Hong, Hawoong [X-Ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA; Rosenberg, Richard A. [X-Ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA; Marks, Laurence D. [Department of Materials Science, Northwestern University, Evanston, Illinois 60202, USA; Fong, Dillon D. [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

2017-12-01

The oxygen sublattice in the complex oxides is typically composed of corner-shared polyhedra, with transition metals at their centers. The electronic and chemical properties of the oxide depend on the type and geometric arrangement of these polyhedra, which can be controlled through epitaxial synthesis. Here, we use oxide molecular beam epitaxy to create SrCoOx:SrTiO3 superlattices with tunable oxygen coordination environments and sublattice geometries. Using soft X-ray spectroscopy, we find that the chemical state of Co can be varied with the polyhedral arrangement, demonstrating a new strategy for achieving unique electronic properties in the transition metal oxides.

Computational Investigation of Amine–Oxygen Exciplex Formation

Science.gov (United States)

Haupert, Levi M.; Simpson, Garth J.; Slipchenko, Lyudmila V.

2012-01-01

It has been suggested that fluorescence from amine-containing dendrimer compounds could be the result of a charge transfer between amine groups and molecular oxygen [Chu, C.-C.; Imae, T. Macromol. Rapid Commun. 2009, 30, 89.]. In this paper we employ equation-of-motion coupled cluster computational methods to study the electronic structure of an ammonia–oxygen model complex to examine this possibility. The results reveal several bound electronic states with charge transfer character with emission energies generally consistent with previous observations. However, further work involving confinement, solvent, and amine structure effects will be necessary for more rigorous examination of the charge transfer fluorescence hypothesis. PMID:21812447

Effect of oxygen atoms dissociated by non-equilibrium plasma on flame of methane oxygen and argon pre-mixture gas

Science.gov (United States)

Akashi, Haruaki; Yoshinaga, Tomokazu; Sasaki, Koichi

2014-10-01

For more efficient way of combustion, plasma-assisted combustion has been investigated by many researchers. But it is very difficult to clarify the effect of plasma even on the flame of methane. Because there are many complex chemical reactions in combustion system. Sasaki et al. has reported that the flame length of methane and air premixed burner shortened by irradiating microwave power. They also measured emission from Second Positive Band System of nitrogen during the irradiation. The emission indicates existence of high energy electrons which are accelerated by the microwave. The high energy electrons also dissociate oxygen molecules easily and oxygen atom would have some effects on the flame. But the dissociation ratio of oxygen molecules by the non-equilibrium plasma is significantly low, compared to that in the combustion reaction. To clarify the effect of dissociated oxygen atoms on the flame, dependence of dissociation ratio of oxygen on the flame has been examined using CHEMKIN. It is found that in the case of low dissociation ratio of 10-6, the ignition of the flame becomes slightly earlier. It is also found that in the case of high dissociation ratio of 10-3, the ignition time becomes significantly earlier by almost half. This work was supported by KAKENHI (22340170).

Resonance assignment of PsbP: an extrinsic protein from photosystem II of Spinacia oleracea

Czech Academy of Sciences Publication Activity Database

Rathner, A.; Chandra, K.; Rathner, P.; Horničáková, M.; Schlagnitweit, J.; Kohoutová, Jaroslava; Ettrich, Rüdiger; Müller, N.

2015-01-01

Roč. 9, č. 2 (2015), s. 341-346 ISSN 1874-2718 Institutional support: RVO:61388971 Keywords : PsbP * Photosystem II * Oxygen evolving complex Subject RIV: EE - Microbiology, Virology Impact factor: 0.687, year: 2015

A new evolutionary system for evolving artificial neural networks.

Science.gov (United States)

Yao, X; Liu, Y

1997-01-01

This paper presents a new evolutionary system, i.e., EPNet, for evolving artificial neural networks (ANNs). The evolutionary algorithm used in EPNet is based on Fogel's evolutionary programming (EP). Unlike most previous studies on evolving ANN's, this paper puts its emphasis on evolving ANN's behaviors. Five mutation operators proposed in EPNet reflect such an emphasis on evolving behaviors. Close behavioral links between parents and their offspring are maintained by various mutations, such as partial training and node splitting. EPNet evolves ANN's architectures and connection weights (including biases) simultaneously in order to reduce the noise in fitness evaluation. The parsimony of evolved ANN's is encouraged by preferring node/connection deletion to addition. EPNet has been tested on a number of benchmark problems in machine learning and ANNs, such as the parity problem, the medical diagnosis problems, the Australian credit card assessment problem, and the Mackey-Glass time series prediction problem. The experimental results show that EPNet can produce very compact ANNs with good generalization ability in comparison with other algorithms.

Structural characterization of the Actinides (III) and (IV) - DOTA complexes

International Nuclear Information System (INIS)

Audras, Matthieu

2014-01-01

The polyamino-carboxylate anions have been identified as compounds of interest in the operations of actinide separation, in actinide migration in the environment and in human radio-toxicology. The structural characterization of complexes formed between actinides and polyamino-carboxylates ligands is essential for a better understanding of actinide-ligands interactions. Among the polyamino-carboxylate anions, the DOTA ligand (1,4,7,10-tetraaza-cyclododecane tetraacetic acid) is described as a very strong complexing agent of the lanthanides(III), but has been little studied with actinides. The objective of this thesis is to describe the complexes formed between the actinides (III) and (IV) and the DOTA ligand, and compare them with the lanthanide complexes. For this, an approach has been introduced to characterize the complexes by complementary analytical techniques (spectrophotometry, electro-spray ionization mass spectrometry, NMR, EXAFS, electrochemistry), but also by calculations of theoretical chemistry to help the interpretation of the experimental data. The formation of a 1:1 complex is observed with the actinides(III) (plutonium and americium) as for lanthanides(III): rapid formation of intermediate species which evolves slowly towards the formation of a limit complex. Within this complex, the cation is located inside the cavity formed by the ligand. Four nitrogen atoms and four oxygen atoms from the carboxylate functions are involved in the coordination sphere of the cation. However, differences were observed in the bond lengths formed between the cation and the nitrogen atoms (the bonds are somewhat shorter in the case of actinide complexes) as well as the complexation kinetics, which is slightly faster for the actinides(III) than for lanthanide(III) ions of equivalent radius. The same behavior was observed in solution upon complexation of actinides(IV) (uranium, plutonium and neptunium): slow formation of a 1:1 complex (actinide(IV):ligand) in wherein the

Spectroscopic Determination of Trace Contaminants in High Purity Oxygen

Science.gov (United States)

Hornung, Steven D.

2011-01-01

Oxygen used for extravehicular activities (EVA) must be free of contaminants because a difference in a few tenths of a percent of argon or nitrogen content can mean significant reduction in available EVA time. These inert gases build up in the extravehicular mobility unit because they are not metabolized or scrubbed from the atmosphere. Measurement of oxygen purity above 99.5% is problematic, and currently only complex instruments such as gas chromatographs or mass spectrometers are used for these determinations. Because liquid oxygen boil-off from the space shuttle will no longer be available to supply oxygen for EVA use, other concepts are being developed to produce and validate high purity oxygen from cabin air aboard the International Space Station. A prototype optical emission technique capable of detecting argon and nitrogen below 0.1% in oxygen was developed at White Sands Test Facility. This instrument uses a glow discharge in reduced pressure gas to produce atomic emission from the species present. Because the atomic emission lines from oxygen, nitrogen, and argon are discrete and in many cases well-separated, trace amounts of argon and nitrogen can be detected in the ultraviolet and visible spectrum. This is a straightforward, direct measurement of the target contaminants and may lend itself to a device capable of on-orbit verification of oxygen purity. System design and optimized measurement parameters are presented.

Surface structural evolvement in the conversion of polyacrylonitrile precursors to carbon fibers

International Nuclear Information System (INIS)

Qian, Xin; Zou, Ruifen; OuYang, Qin; Wang, Xuefei; Zhang, Yonggang

2015-01-01

Highlights: • The characteristic striated topography of PAN precursors resulted from the wet spinning process could pass down to carbon fibers. • The ridges and grooves monitored became much more well-defined after the thermo-oxidation. • Both the depth and the width of longitudinal grooves decreased after the carbonization. • Carbon, nitrogen, oxygen and silicon were the governing elements on the fiber surface. - Abstract: Surface structural evolvement in the conversion of polyacrylonitrile (PAN) precursors to carbon fibers was investigated through scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). SEM results showed that the characteristic striated topography of PAN precursors resulted from the wet spinning process could pass down to carbon fibers. The fiber diameter gradually decreased from 11.3 μm to 5.5 μm and the corresponding density increased from 1.18 g/cm 3 to 1.80 g/cm 3 in the conversion of PAN precursors to carbon fibers. The ridges and grooves monitored by AFM became much more well-defined after the thermo-oxidation. However, the original longitudinal grooves were destroyed and both the depth and the width of longitudinal grooves decreased after the carbonization. XPS results revealed that carbon, nitrogen, oxygen and silicon were the governing elements on the fiber surface. The −C−C functional groups was the dominant groups and the relative contents of −C=O and −COO groups gradually increased in the process of thermo-oxidation and carbonization

Pseudomonas syringae enhances herbivory by suppressing the reactive oxygen burst in Arabidopsis.

Science.gov (United States)

Groen, Simon C; Humphrey, Parris T; Chevasco, Daniela; Ausubel, Frederick M; Pierce, Naomi E; Whiteman, Noah K

2016-01-01

Plant-herbivore interactions have evolved in the presence of plant-colonizing microbes. These microbes can have important third-party effects on herbivore ecology, as exemplified by drosophilid flies that evolved from ancestors feeding on plant-associated microbes. Leaf-mining flies in the genus Scaptomyza, which is nested within the paraphyletic genus Drosophila, show strong associations with bacteria in the genus Pseudomonas, including Pseudomonas syringae. Adult females are capable of vectoring these bacteria between plants and larvae show a preference for feeding on P. syringae-infected leaves. Here we show that Scaptomyza flava larvae can also vector P. syringae to and from feeding sites, and that they not only feed more, but also develop faster on plants previously infected with P. syringae. Our genetic and physiological data show that P. syringae enhances S. flava feeding on infected plants at least in part by suppressing anti-herbivore defenses mediated by reactive oxygen species. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dynamical community structure of populations evolving on genotype networks

International Nuclear Information System (INIS)

Capitán, José A.; Aguirre, Jacobo; Manrubia, Susanna

2015-01-01

Neutral evolutionary dynamics of replicators occurs on large and heterogeneous networks of genotypes. These networks, formed by all genotypes that yield the same phenotype, have a complex architecture that conditions the molecular composition of populations and their movements on genome spaces. Here we consider as an example the case of populations evolving on RNA secondary structure neutral networks and study the community structure of the network revealed through dynamical properties of the population at equilibrium and during adaptive transients. We unveil a rich hierarchical community structure that, eventually, can be traced back to the non-trivial relationship between RNA secondary structure and sequence composition. We demonstrate that usual measures of modularity that only take into account the static, topological structure of networks, cannot identify the community structure disclosed by population dynamics

Catabolite and Oxygen Regulation of Enterohemorrhagic Escherichia coli Virulence

Directory of Open Access Journals (Sweden)

Kimberly M. Carlson-Banning

2016-11-01

Full Text Available The biogeography of the gut is diverse in its longitudinal axis, as well as within specific microenvironments. Differential oxygenation and nutrient composition drive the membership of microbial communities in these habitats. Moreover, enteric pathogens can orchestrate further modifications to gain a competitive advantage toward host colonization. These pathogens are versatile and adept when exploiting the human colon. They expertly navigate complex environmental cues and interkingdom signaling to colonize and infect their hosts. Here we demonstrate how enterohemorrhagic Escherichia coli (EHEC uses three sugar-sensing transcription factors, Cra, KdpE, and FusR, to exquisitely regulate the expression of virulence factors associated with its type III secretion system (T3SS when exposed to various oxygen concentrations. We also explored the effect of mucin-derived nonpreferred carbon sources on EHEC growth and expression of virulence genes. Taken together, the results show that EHEC represses the expression of its T3SS when oxygen is absent, mimicking the largely anaerobic lumen, and activates its T3SS when oxygen is available through Cra. In addition, when EHEC senses mucin-derived sugars heavily present in the O-linked and N-linked glycans of the large intestine, virulence gene expression is initiated. Sugars derived from pectin, a complex plant polysaccharide digested in the large intestine, also increased virulence gene expression. Not only does EHEC sense host- and microbiota-derived interkingdom signals, it also uses oxygen availability and mucin-derived sugars liberated by the microbiota to stimulate expression of the T3SS. This precision in gene regulation allows EHEC to be an efficient pathogen with an extremely low infectious dose.

Mentoring: An Evolving Relationship.

Science.gov (United States)

Block, Michelle; Florczak, Kristine L

2017-04-01

The column concerns itself with mentoring as an evolving relationship between mentor and mentee. The collegiate mentoring model, the transformational transcendence model, and the humanbecoming mentoring model are considered in light of a dialogue with mentors at a Midwest university and conclusions are drawn.

Nonsynonymous substitution rate (Ka is a relatively consistent parameter for defining fast-evolving and slow-evolving protein-coding genes

Directory of Open Access Journals (Sweden)

Wang Lei

2011-02-01

Full Text Available Abstract Background Mammalian genome sequence data are being acquired in large quantities and at enormous speeds. We now have a tremendous opportunity to better understand which genes are the most variable or conserved, and what their particular functions and evolutionary dynamics are, through comparative genomics. Results We chose human and eleven other high-coverage mammalian genome data–as well as an avian genome as an outgroup–to analyze orthologous protein-coding genes using nonsynonymous (Ka and synonymous (Ks substitution rates. After evaluating eight commonly-used methods of Ka and Ks calculation, we observed that these methods yielded a nearly uniform result when estimating Ka, but not Ks (or Ka/Ks. When sorting genes based on Ka, we noticed that fast-evolving and slow-evolving genes often belonged to different functional classes, with respect to species-specificity and lineage-specificity. In particular, we identified two functional classes of genes in the acquired immune system. Fast-evolving genes coded for signal-transducing proteins, such as receptors, ligands, cytokines, and CDs (cluster of differentiation, mostly surface proteins, whereas the slow-evolving genes were for function-modulating proteins, such as kinases and adaptor proteins. In addition, among slow-evolving genes that had functions related to the central nervous system, neurodegenerative disease-related pathways were enriched significantly in most mammalian species. We also confirmed that gene expression was negatively correlated with evolution rate, i.e. slow-evolving genes were expressed at higher levels than fast-evolving genes. Our results indicated that the functional specializations of the three major mammalian clades were: sensory perception and oncogenesis in primates, reproduction and hormone regulation in large mammals, and immunity and angiotensin in rodents. Conclusion Our study suggests that Ka calculation, which is less biased compared to Ks and Ka

Accelerated proteomic visualization of individual predatory venoms of Conus purpurascens reveals separately evolved predation-evoked venom cabals.

Science.gov (United States)

Himaya, S W A; Marí, Frank; Lewis, Richard J

2018-01-10

Cone snail venoms have separately evolved for predation and defense. Despite remarkable inter- and intra-species variability, defined sets of synergistic venom peptides (cabals) are considered essential for prey capture by cone snails. To better understand the role of predatory cabals in cone snails, we used a high-throughput proteomic data mining and visualisation approach. Using this approach, the relationship between the predatory venom peptides from nine C. purpurascens was systematically analysed. Surprisingly, potentially synergistic levels of κ-PVIIA and δ-PVIA were only identified in five of nine specimens. In contrast, the remaining four specimens lacked significant levels of these known excitotoxins and instead contained high levels of the muscle nAChR blockers ψ-PIIIE and αA-PIVA. Interestingly, one of nine specimens expressed both cabals, suggesting that these sub-groups might represent inter-breeding sub-species of C. purpurascens. High throughput cluster analysis also revealed these two cabals clustered with distinct groups of venom peptides that are presently uncharacterised. This is the first report showing that the cone snails of the same species can deploy two separate and distinct predatory cabals for prey capture and shows that the cabals deployed by this species can be more complex than presently realized. Our semi-automated proteomic analysis facilitates the deconvolution of complex venoms to identify co-evolved families of peptides and help unravel their evolutionary relationships in complex venoms.

Interactively Evolving Compositional Sound Synthesis Networks

DEFF Research Database (Denmark)

Jónsson, Björn Þór; Hoover, Amy K.; Risi, Sebastian

2015-01-01

the space of potential sounds that can be generated through such compositional sound synthesis networks (CSSNs). To study the effect of evolution on subjective appreciation, participants in a listener study ranked evolved timbres by personal preference, resulting in preferences skewed toward the first......While the success of electronic music often relies on the uniqueness and quality of selected timbres, many musicians struggle with complicated and expensive equipment and techniques to create their desired sounds. Instead, this paper presents a technique for producing novel timbres that are evolved...

Gene expression changes in the injured spinal cord following transplantation of mesenchymal stem cells or olfactory ensheathing cells.

Directory of Open Access Journals (Sweden)

Abel Torres-Espín

Full Text Available Transplantation of bone marrow derived mesenchymal stromal cells (MSC or olfactory ensheathing cells (OEC have demonstrated beneficial effects after spinal cord injury (SCI, providing tissue protection and improving the functional recovery. However, the changes induced by these cells after their transplantation into the injured spinal cord remain largely unknown. We analyzed the changes in the spinal cord transcriptome after a contusion injury and MSC or OEC transplantation. The cells were injected immediately or 7 days after the injury. The mRNA of the spinal cord injured segment was extracted and analyzed by microarray at 2 and 7 days after cell grafting. The gene profiles were analyzed by clustering and functional enrichment analysis based on the Gene Ontology database. We found that both MSC and OEC transplanted acutely after injury induce an early up-regulation of genes related to tissue protection and regeneration. In contrast, cells transplanted at 7 days after injury down-regulate genes related to tissue regeneration. The most important change after MSC or OEC transplant was a marked increase in expression of genes associated with foreign body response and adaptive immune response. These data suggest a regulatory effect of MSC and OEC transplantation after SCI regarding tissue repair processes, but a fast rejection response to the grafted cells. Our results provide an initial step to determine the mechanisms of action and to optimize cell therapy for SCI.

The Evolving Role of Selenium in the Treatment of Graves' Disease and Ophthalmopathy

OpenAIRE

Duntas, Leonidas H.

2012-01-01

Graves' disease (GD) and ophthalmopathy (GO) are organ-specific autoimmune-inflammatory disorders characterized by a complex pathogenesis. The inflammatory process is dominated by an imbalance of the antioxidant-oxidant mechanism, increased production of radical oxygen species (ROS), and cytokines which sustain the autoimmune process and perpetuate the disease. Recently, selenium, which is a powerful antioxidant, has been successfully applied in patients with mild GO, slowing the progression ...

Evolving effective incremental SAT solvers with GP

OpenAIRE

Bader, Mohamed; Poli, R.

2008-01-01

Hyper-Heuristics could simply be defined as heuristics to choose other heuristics, and it is a way of combining existing heuristics to generate new ones. In a Hyper-Heuristic framework, the framework is used for evolving effective incremental (Inc*) solvers for SAT. We test the evolved heuristics (IncHH) against other known local search heuristics on a variety of benchmark SAT problems.

Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

International Nuclear Information System (INIS)

Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

2015-01-01

Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

Removing oxygen from a solvent extractant in an uranium recovery process

International Nuclear Information System (INIS)

Hurst, F.J.; Brown, G.M.; Posey, F.A.

1984-01-01

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous and accumulation of complex iron phosphates or cruds

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

Science.gov (United States)

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

Influence of oxygen impurity atoms on defect clusters and radiation hardening in neutron-irradiated vanadium

International Nuclear Information System (INIS)

Bajaj, R.; Wechsler, M.S.

1975-01-01

Single crystal TEM samples and polycrystalline tensile samples of vanadium containing 60-640 wt ppm oxygen were irradiated at about 100 0 C to about 1.3 x 10 19 neutrons/cm 2 (E greater than 1 MeV) and post-irradiation annealed up to 800 0 C. The defect cluster density increased and the average size decreased with increasing oxygen concentration. Higher oxygen concentrations caused the radiation hardening and radiation-anneal hardening to increase. The observations are consistent with the nucleation of defect clusters by small oxygen or oxygen-point defect complexes and the trapping of oxygen at defect clusters upon post-irradiation annealing

Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

Science.gov (United States)

González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

2014-08-07

In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

Eyes on the prize: reflections on the impact of the evolving digital ecology on the librarian as expert intermediary and knowledge coach, 1969-2009.

Science.gov (United States)

Homan, J Michael

2010-01-01

The 2009 Janet Doe Lecture reflects on the continuing value and increasing return on investment of librarian-mediated services in the constantly evolving digital ecology and complex knowledge environment of the health sciences. The interrelationship of knowledge, decision making based on knowledge, technology used to access and retrieve knowledge, and the important linkage roles of expert librarian intermediaries is examined. Professional experiences from 1969 to 2009, occurring during a time of unprecedented changes in the digital ecology of librarianship, are the base on which the evolving role and value of librarians as knowledge coaches and expert intermediaries are examined. Librarian-mediated services linking knowledge and critical decision making in health care have become more valuable than ever as technology continues to reshape an increasingly complex knowledge environment.

No oxygen? No problem! Intrinsic brain tolerance to hypoxia in vertebrates

Science.gov (United States)

Larson, John; Drew, Kelly L.; Folkow, Lars P.; Milton, Sarah L.; Park, Thomas J.

2014-01-01

Many vertebrates are challenged by either chronic or acute episodes of low oxygen availability in their natural environments. Brain function is especially vulnerable to the effects of hypoxia and can be irreversibly impaired by even brief periods of low oxygen supply. This review describes recent research on physiological mechanisms that have evolved in certain vertebrate species to cope with brain hypoxia. Four model systems are considered: freshwater turtles that can survive for months trapped in frozen-over lakes, arctic ground squirrels that respire at extremely low rates during winter hibernation, seals and whales that undertake breath-hold dives lasting minutes to hours, and naked mole-rats that live in crowded burrows completely underground for their entire lives. These species exhibit remarkable specializations of brain physiology that adapt them for acute or chronic episodes of hypoxia. These specializations may be reactive in nature, involving modifications to the catastrophic sequelae of oxygen deprivation that occur in non-tolerant species, or preparatory in nature, preventing the activation of those sequelae altogether. Better understanding of the mechanisms used by these hypoxia-tolerant vertebrates will increase appreciation of how nervous systems are adapted for life in specific ecological niches as well as inform advances in therapy for neurological conditions such as stroke and epilepsy. PMID:24671961

The Role of Oxygen Sensors, Hydroxylases, and HIF in Cardiac Function and Disease

Directory of Open Access Journals (Sweden)

W. H. Davin Townley-Tilson

2015-01-01

Full Text Available Ischemic heart disease is the leading cause of death worldwide. Oxygen-sensing proteins are critical components of the physiological response to hypoxia and reperfusion injury, but the role of oxygen and oxygen-mediated effects is complex in that they can be cardioprotective or deleterious to the cardiac tissue. Over 200 oxygen-sensing proteins mediate the effects of oxygen tension and use oxygen as a substrate for posttranslational modification of other proteins. Hydroxylases are an essential component of these oxygen-sensing proteins. While a major role of hydroxylases is regulating the transcription factor HIF, we investigate the increasing scope of hydroxylase substrates. This review discusses the importance of oxygen-mediated effects in the heart as well as how the field of oxygen-sensing proteins is expanding, providing a more complete picture into how these enzymes play a multifaceted role in cardiac function and disease. We also review how oxygen-sensing proteins and hydroxylase function could prove to be invaluable in drug design and therapeutic targets for heart disease.

Evolving Intelligent Systems Methodology and Applications

CERN Document Server

Angelov, Plamen; Kasabov, Nik

2010-01-01

From theory to techniques, the first all-in-one resource for EIS. There is a clear demand in advanced process industries, defense, and Internet and communication (VoIP) applications for intelligent yet adaptive/evolving systems. Evolving Intelligent Systems is the first self- contained volume that covers this newly established concept in its entirety, from a systematic methodology to case studies to industrial applications. Featuring chapters written by leading world experts, it addresses the progress, trends, and major achievements in this emerging research field, with a strong emphasis on th

ASP project. Dissolved oxygen issues in ASP project

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M.Y. Bondar

2018-03-01

Full Text Available The article presents the latest results of studies about the effect of dissolved oxygen on the efficiency of the ASP flooding project implemented by Salym Petroleum Development N.V.. Pilot project on experimental injection of anionic surfactant solutions, soda and polymer into the reservoir for enhanced oil recovery (ASP project has been implemented since 2016. The stability of one of the components of the ASP polymer is strongly dependent on the presence of iron, stiffness cations and dissolved oxygen in the water. Since the polymer is used for injection at two stages of the project, which are essential and the longest, at the design stage of ASP project a whole complex of polymer protection had been established against negative factors, in particular from the influence of oxygen, which causes not only oxygen corrosion but also irreversible destruction polymer chains. In the paper, studies on the stability of polymer solutions are described, an analysis of viscosity loss with time in the presence of iron and oxygen for polymer solutions is carried out. The choice of chemical deoxygenation method for the control of dissolved oxygen is substantiated. The program of laboratory studies of the ASP project and the analytical instruments used are described. The technological scheme of the ASP process is presented, and recommendations for the implementation of the technology are given.

Methods Evolved by Observation

Science.gov (United States)

Montessori, Maria

2016-01-01

Montessori's idea of the child's nature and the teacher's perceptiveness begins with amazing simplicity, and when she speaks of "methods evolved," she is unveiling a methodological system for observation. She begins with the early childhood explosion into writing, which is a familiar child phenomenon that Montessori has written about…

Adult venovenous extracorporeal membrane oxygenation for severe respiratory failure: Current status and future perspectives

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Ayan Sen

2016-01-01

Full Text Available Extracorporeal membrane oxygenation (ECMO for severe acute respiratory failure was proposed more than 40 years ago. Despite the publication of the ARDSNet study and adoption of lung protective ventilation, the mortality for acute respiratory failure due to acute respiratory distress syndrome has continued to remain high. This technology has evolved over the past couple of decades and has been noted to be safe and successful, especially during the worldwide H1N1 influenza pandemic with good survival rates. The primary indications for ECMO in acute respiratory failure include severe refractory hypoxemic and hypercarbic respiratory failure in spite of maximum lung protective ventilatory support. Various triage criteria have been described and published. Contraindications exist when application of ECMO may be futile or technically impossible. Knowledge and appreciation of the circuit, cannulae, and the physiology of gas exchange with ECMO are necessary to ensure lung rest, efficiency of oxygenation, and ventilation as well as troubleshooting problems. Anticoagulation is a major concern with ECMO, and the evidence is evolving with respect to diagnostic testing and use of anticoagulants. Clinical management of the patient includes comprehensive critical care addressing sedation and neurologic issues, ensuring lung recruitment, diuresis, early enteral nutrition, treatment and surveillance of infections, and multisystem organ support. Newer technology that delinks oxygenation and ventilation by extracorporeal carbon dioxide removal may lead to ultra-lung protective ventilation, avoidance of endotracheal intubation in some situations, and ambulatory therapies as a bridge to lung transplantation. Risks, complications, and long-term outcomes and resources need to be considered and weighed in before widespread application. Ethical challenges are a reality and a multidisciplinary approach that should be adopted for every case in consideration.

Evolved-Lithology Clasts in Lunar Breccias: Relating Petrogenetic Diversity to Measured Water Content

Science.gov (United States)

Christoffersen, R.; Simon, J. J.; Ross, D. K.

2017-01-01

Studies of the inventory and distribution of water in lunar rocks have recently begun to focus on alkali suite samples as possible water repositories, particularly the most highly evolved granitoid lithologies. Although H analyses of feldspars in these rocks have so far pointed to 'low' (less than 20 ppm) H2O contents, there is sufficient variability in the dataset (e.g., 2-20 ppm) to warrant consideration of the petrogenetic factors that may have caused some granitoid-to-intermediate rocks to be dryer or wetter than others. Given that all examples of these rocks occur as clasts in complex impact breccias, the role of impact and other factors in altering water contents established by primary igneous processes becomes a major factor. We are supporting our ongoing SIMS studies of water in evolved lunar lithologies with systematic SEM and EPMA observations. Here we report a synthesis of the observations as part of developing discriminating factors for reconstructing the thermal, crystallization and shock history of these samples as compared with their water contents.

Oxygen as a driver of early arthropod micro-benthos evolution.

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Mark Williams

Full Text Available BACKGROUND: We examine the physiological and lifestyle adaptations which facilitated the emergence of ostracods as the numerically dominant Phanerozoic bivalve arthropod micro-benthos. METHODOLOGY/PRINCIPAL FINDINGS: The PO(2 of modern normoxic seawater is 21 kPa (air-equilibrated water, a level that would cause cellular damage if found in the tissues of ostracods and much other marine fauna. The PO(2 of most aquatic breathers at the cellular level is much lower, between 1 and 3 kPa. Ostracods avoid oxygen toxicity by migrating to waters which are hypoxic, or by developing metabolisms which generate high consumption of O(2. Interrogation of the Cambrian record of bivalve arthropod micro-benthos suggests a strong control on ecosystem evolution exerted by changing seawater O(2 levels. The PO(2 of air-equilibrated Cambrian-seawater is predicted to have varied between 10 and 30 kPa. Three groups of marine shelf-dwelling bivalve arthropods adopted different responses to Cambrian seawater O(2. Bradoriida evolved cardiovascular systems that favoured colonization of oxygenated marine waters. Their biodiversity declined during intervals associated with black shale deposition and marine shelf anoxia and their diversity may also have been curtailed by elevated late Cambrian (Furongian oxygen-levels that increased the PO(2 gradient between seawater and bradoriid tissues. Phosphatocopida responded to Cambrian anoxia differently, reaching their peak during widespread seabed dysoxia of the SPICE event. They lacked a cardiovascular system and appear to have been adapted to seawater hypoxia. As latest Cambrian marine shelf waters became well oxygenated, phosphatocopids went extinct. Changing seawater oxygen-levels and the demise of much of the seabed bradoriid micro-benthos favoured a third group of arthropod micro-benthos, the ostracods. These animals adopted lifestyles that made them tolerant of changes in seawater O(2. Ostracods became the numerically

Evolving artificial metalloenzymes via random mutagenesis

Science.gov (United States)

Yang, Hao; Swartz, Alan M.; Park, Hyun June; Srivastava, Poonam; Ellis-Guardiola, Ken; Upp, David M.; Lee, Gihoon; Belsare, Ketaki; Gu, Yifan; Zhang, Chen; Moellering, Raymond E.; Lewis, Jared C.

2018-03-01

Random mutagenesis has the potential to optimize the efficiency and selectivity of protein catalysts without requiring detailed knowledge of protein structure; however, introducing synthetic metal cofactors complicates the expression and screening of enzyme libraries, and activity arising from free cofactor must be eliminated. Here we report an efficient platform to create and screen libraries of artificial metalloenzymes (ArMs) via random mutagenesis, which we use to evolve highly selective dirhodium cyclopropanases. Error-prone PCR and combinatorial codon mutagenesis enabled multiplexed analysis of random mutations, including at sites distal to the putative ArM active site that are difficult to identify using targeted mutagenesis approaches. Variants that exhibited significantly improved selectivity for each of the cyclopropane product enantiomers were identified, and higher activity than previously reported ArM cyclopropanases obtained via targeted mutagenesis was also observed. This improved selectivity carried over to other dirhodium-catalysed transformations, including N-H, S-H and Si-H insertion, demonstrating that ArMs evolved for one reaction can serve as starting points to evolve catalysts for others.

Why did heterospory evolve?

Science.gov (United States)

Petersen, Kurt B; Burd, Martin

2017-08-01

The primitive land plant life cycle featured the production of spores of unimodal size, a condition called homospory. The evolution of bimodal size distributions with small male spores and large female spores, known as heterospory, was an innovation that occurred repeatedly in the history of land plants. The importance of desiccation-resistant spores for colonization of the land is well known, but the adaptive value of heterospory has never been well established. It was an addition to a sexual life cycle that already involved male and female gametes. Its role as a precursor to the evolution of seeds has received much attention, but this is an evolutionary consequence of heterospory that cannot explain the transition from homospory to heterospory (and the lack of evolutionary reversal from heterospory to homospory). Enforced outcrossing of gametophytes has often been mentioned in connection to heterospory, but we review the shortcomings of this argument as an explanation of the selective advantage of heterospory. Few alternative arguments concerning the selective forces favouring heterospory have been proposed, a paucity of attention that is surprising given the importance of this innovation in land plant evolution. In this review we highlight two ideas that may lead us to a better understanding of why heterospory evolved. First, models of optimal resource allocation - an approach that has been used for decades in evolutionary ecology to help understand parental investment and other life-history patterns - suggest that an evolutionary increase in spore size could reach a threshold at which small spores yielding small, sperm-producing gametophytes would return greater fitness per unit of resource investment than would large spores and bisexual gametophytes. With the advent of such microspores, megaspores would evolve under frequency-dependent selection. This argument can account for the appearance of heterospory in the Devonian, when increasingly tall and complex

Oxygen toxicity

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C. A. van der Westhuizen

1990-07-01

Full Text Available Oxygen has been discovered about 200 years ago. Since then the vital physiological involvement of oxygen in various biologi­cal processes, mainly energy production, has been established. However, in the body molecular oxygen can be converted to toxic oxygen metabolites such as superoxide anion, hydrogen peroxide, the hydroxyl radical and singlet oxygen. These toxic metabolites are produced mainly in the mitochondria, plasma membranes and endoplasmic reticulum.

The evolution of resource adaptation: how generalist and specialist consumers evolve.

Science.gov (United States)

Ma, Junling; Levin, Simon A

2006-07-01

Why and how specialist and generalist strategies evolve are important questions in evolutionary ecology. In this paper, with the method of adaptive dynamics and evolutionary branching, we identify conditions that select for specialist and generalist strategies. Generally, generalist strategies evolve if there is a switching benefit; specialists evolve if there is a switching cost. If the switching cost is large, specialists always evolve. If the switching cost is small, even though the consumer will first evolve toward a generalist strategy, it will eventually branch into two specialists.

An evolving network model with modular growth

International Nuclear Information System (INIS)

Zou Zhi-Yun; Liu Peng; Lei Li; Gao Jian-Zhi

2012-01-01

In this paper, we propose an evolving network model growing fast in units of module, according to the analysis of the evolution characteristics in real complex networks. Each module is a small-world network containing several interconnected nodes and the nodes between the modules are linked by preferential attachment on degree of nodes. We study the modularity measure of the proposed model, which can be adjusted by changing the ratio of the number of inner-module edges and the number of inter-module edges. In view of the mean-field theory, we develop an analytical function of the degree distribution, which is verified by a numerical example and indicates that the degree distribution shows characteristics of the small-world network and the scale-free network distinctly at different segments. The clustering coefficient and the average path length of the network are simulated numerically, indicating that the network shows the small-world property and is affected little by the randomness of the new module. (interdisciplinary physics and related areas of science and technology)

Methanol Formation via Oxygen Insertion Chemistry in Ices

Science.gov (United States)

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

2017-08-01

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH4: ˜65% of insertions lead to CH3OH, with the remainder leading instead to H2CO formation. There is no evidence for CH3 or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH3OH formation from O2 and CH4 diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Methanol Formation via Oxygen Insertion Chemistry in Ices

Energy Technology Data Exchange (ETDEWEB)

Bergner, Jennifer B. [Harvard University Department of Chemistry and Chemical Biology, 10 Oxford Street, Cambridge, MA 02138 (United States); Öberg, Karin I.; Rajappan, Mahesh [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2017-08-10

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O{sub 2} within a mixture of O{sub 2}:CH{sub 4} and observe efficient production of CH{sub 3}OH via O({sup 1}D) insertion. CH{sub 3}OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH{sub 4}: ∼65% of insertions lead to CH{sub 3}OH, with the remainder leading instead to H{sub 2}CO formation. There is no evidence for CH{sub 3} or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH{sub 3}OH formation from O{sub 2} and CH{sub 4} diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Individual Differences in Students' Complex Problem Solving Skills: How They Evolve and What They Imply

Science.gov (United States)

Wüstenberg, Sascha; Greiff, Samuel; Vainikainen, Mari-Pauliina; Murphy, Kevin

2016-01-01

Changes in the demands posed by increasingly complex workplaces in the 21st century have raised the importance of nonroutine skills such as complex problem solving (CPS). However, little is known about the antecedents and outcomes of CPS, especially with regard to malleable external factors such as classroom climate. To investigate the relations…

Modular interdependency in complex dynamical systems.

Science.gov (United States)

Watson, Richard A; Pollack, Jordan B

2005-01-01

Herbert A. Simon's characterization of modularity in dynamical systems describes subsystems as having dynamics that are approximately independent of those of other subsystems (in the short term). This fits with the general intuition that modules must, by definition, be approximately independent. In the evolution of complex systems, such modularity may enable subsystems to be modified and adapted independently of other subsystems, whereas in a nonmodular system, modifications to one part of the system may result in deleterious side effects elsewhere in the system. But this notion of modularity and its effect on evolvability is not well quantified and is rather simplistic. In particular, modularity need not imply that intermodule dependences are weak or unimportant. In dynamical systems this is acknowledged by Simon's suggestion that, in the long term, the dynamical behaviors of subsystems do interact with one another, albeit in an "aggregate" manner--but this kind of intermodule interaction is omitted in models of modularity for evolvability. In this brief discussion we seek to unify notions of modularity in dynamical systems with notions of how modularity affects evolvability. This leads to a quantifiable measure of modularity and a different understanding of its effect on evolvability.

Adaptation of Escherichia coli to glucose promotes evolvability in lactose.

Science.gov (United States)

Phillips, Kelly N; Castillo, Gerardo; Wünsche, Andrea; Cooper, Tim F

2016-02-01

The selective history of a population can influence its subsequent evolution, an effect known as historical contingency. We previously observed that five of six replicate populations that were evolved in a glucose-limited environment for 2000 generations, then switched to lactose for 1000 generations, had higher fitness increases in lactose than populations started directly from the ancestor. To test if selection in glucose systematically increased lactose evolvability, we started 12 replay populations--six from a population subsample and six from a single randomly selected clone--from each of the six glucose-evolved founder populations. These replay populations and 18 ancestral populations were evolved for 1000 generations in a lactose-limited environment. We found that replay populations were initially slightly less fit in lactose than the ancestor, but were more evolvable, in that they increased in fitness at a faster rate and to higher levels. This result indicates that evolution in the glucose environment resulted in genetic changes that increased the potential of genotypes to adapt to lactose. Genome sequencing identified four genes--iclR, nadR, spoT, and rbs--that were mutated in most glucose-evolved clones and are candidates for mediating increased evolvability. Our results demonstrate that short-term selective costs during selection in one environment can lead to changes in evolvability that confer longer term benefits. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Evolving fuzzy rules for relaxed-criteria negotiation.

Science.gov (United States)

Sim, Kwang Mong

2008-12-01

In the literature on automated negotiation, very few negotiation agents are designed with the flexibility to slightly relax their negotiation criteria to reach a consensus more rapidly and with more certainty. Furthermore, these relaxed-criteria negotiation agents were not equipped with the ability to enhance their performance by learning and evolving their relaxed-criteria negotiation rules. The impetus of this work is designing market-driven negotiation agents (MDAs) that not only have the flexibility of relaxing bargaining criteria using fuzzy rules, but can also evolve their structures by learning new relaxed-criteria fuzzy rules to improve their negotiation outcomes as they participate in negotiations in more e-markets. To this end, an evolutionary algorithm for adapting and evolving relaxed-criteria fuzzy rules was developed. Implementing the idea in a testbed, two kinds of experiments for evaluating and comparing EvEMDAs (MDAs with relaxed-criteria rules that are evolved using the evolutionary algorithm) and EMDAs (MDAs with relaxed-criteria rules that are manually constructed) were carried out through stochastic simulations. Empirical results show that: 1) EvEMDAs generally outperformed EMDAs in different types of e-markets and 2) the negotiation outcomes of EvEMDAs generally improved as they negotiated in more e-markets.

Clinical studies with high flow nasal cannula oxygen delivery in 2015

Directory of Open Access Journals (Sweden)

David Sotello

2016-04-01

Full Text Available HFNC devices can provide humidified oxygen at high flow rates with high FiO2s.  This method of oxygen delivery appears to be more comfortable than using noninvasive ventilation, and it does improve oxygenation, reduce respiratory rates, and reduce the sense of dyspnea.  This modality has been studied most in patients with acute hypoxemic respiratory failure. The study reported by Frat et al provides good evidence that patients with moderate to severe respiratory failure (PaO2/FiO2 < 200 may benefit the most. The more complex the patient’s underlying medical problems are the more likely HFNC therapy to fail

Understanding dynamic friction through spontaneously evolving laboratory earthquakes.

Science.gov (United States)

Rubino, V; Rosakis, A J; Lapusta, N

2017-06-29

Friction plays a key role in how ruptures unzip faults in the Earth's crust and release waves that cause destructive shaking. Yet dynamic friction evolution is one of the biggest uncertainties in earthquake science. Here we report on novel measurements of evolving local friction during spontaneously developing mini-earthquakes in the laboratory, enabled by our ultrahigh speed full-field imaging technique. The technique captures the evolution of displacements, velocities and stresses of dynamic ruptures, whose rupture speed range from sub-Rayleigh to supershear. The observed friction has complex evolution, featuring initial velocity strengthening followed by substantial velocity weakening. Our measurements are consistent with rate-and-state friction formulations supplemented with flash heating but not with widely used slip-weakening friction laws. This study develops a new approach for measuring local evolution of dynamic friction and has important implications for understanding earthquake hazard since laws governing frictional resistance of faults are vital ingredients in physically-based predictive models of the earthquake source.

Mixed oxygen ion/electron-conducting ceramics for oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L. [Pacific Northwest National Lab., Richland, WA (United States)

1996-08-01

Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

A brief clinical case of monitoring of oxygenator performance and patient-machine interdependency during prolonged veno-venous extracorporeal membrane oxygenation.

Science.gov (United States)

Belliato, Mirko; Degani, Antonella; Buffa, Antonino; Sciutti, Fabio; Pagani, Michele; Pellegrini, Carlo; Iotti, Giorgio Antonio

2017-10-01

Monitoring veno-venous extracorporeal membrane oxygenation (vvECMO) during 76 days of continuous support in a 42-years old patient with end-stage pulmonary disease, listed for double-lung transplantation. Applying a new monitor (Landing ® , Eurosets, Medolla, Italy) and describing how measured and calculated parameters can be used to understand the variable interdependency between artificial membrane lung (ML) and patient native lung (NL). During vvECMO, in order to understand how the respiratory function is shared between ML and NL, ideally we should obtain data about oxygen transfer and CO 2 removal, both by ML and NL. Measurements for NL can be made on the mechanical ventilator. Measurements for ML are typically made from gas analysis on blood samples drawn from the ECMO system before and after the oxygenator, and therefore are non-continuous. Differently, the Landing monitor provides a continuous measurement of the oxygen transfer from the ML, combined with hemoglobin level, saturation of drained blood and saturation of reinfused blood. Moreover, the Landing monitor provides hemodynamics data about circulation through the ECMO system, with blood flow, pre-oxygenator pressure and post-oxygenator pressure. Of note, measurements include the drain negative pressure, whose monitoring may be particularly useful to prevent hemolysis. Real-time monitoring of vvECMO provides data helpful to understand the complex picture of a patient with severely damaged lungs on one side and an artificial lung on the other side. Data from vvECMO monitoring may help to adapt the settings of both mechanical ventilator and vvECMO. Data about oxygen transfer by the oxygenator are important to evaluate the performance of the device and may help to avoid unnecessary replacements, thus reducing risks and costs.

DrawCompileEvolve: Sparking interactive evolutionary art with human creations

DEFF Research Database (Denmark)

Zhang, Jinhong; Taarnby, Rasmus; Liapis, Antonios

2015-01-01

This paper presents DrawCompileEvolve, a web-based drawing tool which allows users to draw simple primitive shapes, group them together or define patterns in their groupings (e.g. symmetry, repetition). The user’s vector drawing is then compiled into an indirectly encoded genetic representation......, which can be evolved interactively, allowing the user to change the image’s colors, patterns and ultimately transform it. The human artist has direct control while drawing the initial seed of an evolutionary run and indirect control while interactively evolving it, thus making DrawCompileEvolve a mixed...

A simplified concept for controlling oxygen mixtures in the anaesthetic machine--better, cheaper and more user-friendly?

Science.gov (United States)

Berge, J A; Gramstad, L; Grimnes, S

1995-05-01

Modern anaesthetic machines are equipped with several safety components to prevent delivery of hypoxic mixtures. However, such a technical development has increased the complexity of the equipment. We report a reconstructed anaesthetic machine in which a paramagnetic oxygen analyzer has provided the means to simplify the apparatus. The new machine is devoid of several components conventionally included to prevent hypoxic mixtures: oxygen failure protection device, reservoir O2 alarm, N2O/air selector, and proportioning system for oxygen/nitrous oxide delivery. These devices have been replaced by a simple safety system using a paramagnetic oxygen analyzer at the common gas outlet, which in a feed-back system cuts off the supply of nitrous oxide whenever the oxygen concentration falls below 25%. The simplified construction of the anaesthetic machine has important consequences for safety, cost and user-friendliness. Reducing the complexity of the construction also simplifies the pre-use checkout procedure, and an efficient 5-point check list is presented for the new machine.

Zr (IV COMPLEXES OF SOME NITROGEN-OXYGEN DONOR LIGANDS (SEMICARBAZONES & SALICYLALDAZINE

Directory of Open Access Journals (Sweden)

Z F DAWOOD

2002-06-01

Full Text Available Complexes containing mixed ligands of zirconium (IV have been synthesized by the reaction of zirconium (IV nitrate (Zr(NO34, 5H2O with salicylaldazine (SAH2 and semicarbazone ligands benzaldehyde semicarbazone (BSCH, 4-methoxybenzaldehyde semicarbzone (MBSCH, 2-chlorobenzaldehyde semicrbazone (CISCH and cinnamaldehyde semicarbazone (CinSCH forming complexes of the type [Zr2(SAH2(SCH2](NO38 and [Zr2(SA2 (SC2](NO32 in neutral and basic medium respectively. The ligands and their complexes are characterized physico-chemically.

A fibre optic oxygen sensor for monitoring of human breathing

Science.gov (United States)

Chen, Rongsheng; Farmery, Andrew D.; Chen, Rui; Hahn, Clive E. W.

2011-11-01

A reliable and cost effective fibre optic oxygen sensor for monitoring of human breathing has been developed using a normal 200μm silica core/silica cladding optical fibre and a polymer sensing matrix. The fibre optic oxygen sensor is based on the fluorescence quenching of a fluorophore by oxygen. The sensing matrix, containing immobilized Pt(II) complexes, was coated at the end of the silica core/silica cladding optical fibre. The sensitivity and time response of the sensor were evaluated using the method of luminescence lifetime measurement. The polymer substrate influence on the time response of the sensor was improved by using a fibre taper design, and the response time of the optimized sensor was less than 200ms. This silica fibre based optic oxygen sensor is suitable for monitoring of patient breathing in intensive care unit in terms of safety and low cost.

Solar-wind interactions with the Moon: role of oxygen ions

International Nuclear Information System (INIS)

Mukherjee, N.R.

1979-01-01

The solar-wind interacts directly with the lunar surface due to tenuous atmosphere and magnetic field. The interaction results in an almost complete absorption of the solar-wind corpuscles producing no upstream bowshock but a cavity downstream. The solar-wind oxygen ionic species induce and undergo a complex set of reactions with the elements of the lunar minerals and the solar-wind derived trapped gases. In this paper, the long-term concentration and the role of oxygen derived from the solar-wind is discussed. (Auth.)

Evolving and energy dependent optical model description of heavy-ion elastic scattering

International Nuclear Information System (INIS)

Michaelian, K.

1996-01-01

We present the application of a genetic algorithm to the problem of determining an energy dependent optical model description of heavy-ion elastic scattering. The problem requires a search for the global best optical model potential and its energy dependence in a very rugged 12 dimensional parameter space of complex topographical features with many local minima. Random solutions are created in the first generation. The fitness of a solution is related to the χ 2 fit of the calculated differential cross sections with the experimental data. Best fit solutions are evolved through cross over and mutation following the biological example. This genetic algorithm approach combined with local gradient minimization is shown to provide a global, complete and extremely efficient search method, well adapted to complex fitness landscapes. These characteristics, combined with the facility of application, should make it the search method of choice for a wide variety of problems from nuclear physics. (Author)

Modelling long-term redox processes and oxygen scavenging in fractured crystalline rocks

International Nuclear Information System (INIS)

Sidborn, Magnus

2007-10-01

Advanced plans for the construction of a deep geological repository for highly radioactive wastes from nuclear power plants have evolved during the past decades in many countries including Sweden. As part of the Swedish concept, the waste is to be encapsulated in canisters surrounded by low permeability backfill material. The copper canisters will be deposited at around 500 metres depth in granitic rock, which acts as a natural barrier for the transport of radionuclides to the ground surface. These natural and engineered barriers are chosen and designed to ensure the safety of the repository over hundred of thousands of years. One issue of interest for the safety assessment of such a repository is the redox evolution over long times. An oxidising environment would enhance the corrosion of the copper canisters, and increases the mobility of any released radionuclides. In the first part of the present thesis, the ability of the host rock to ensure a reducing environment at repository depth over long times was studied. A model framework was developed with the aim to capture all processes that are deemed to be important for the scavenging of intruding oxygen from the ground surface over long times. Simplifications allowing for analytical solutions were introduced for transparency reasons so that evaluation of results is straight-forward, and so that uncertain parameter values easily can be adjusted. More complex systems were solved numerically for cases when the analytical simplifications are not applicable, and to validate the simplifications underlying the analytical solutions. Results were presented for prevailing present day conditions as well as for conditions deemed to be likely during the melting phase of a period of glaciation. It was shown that the hydraulic properties have a great influence on the oxygen intrusion length downstream along flow-paths in the rock. An important parameter that determines the extent of interaction between the dissolved oxygen and

Crude Fucoidan Extracts Impair Angiogenesis in Models Relevant for Bone Regeneration and Osteosarcoma via Reduction of VEGF and SDF-1

Directory of Open Access Journals (Sweden)

Fanlu Wang

2017-06-01

Full Text Available The marine origin polysaccharide fucoidan combines multiple biological activities. As demonstrated by various studies in vitro and in vivo, fucoidans show anti-viral, anti-tumor, anti-oxidant, anti-inflammatory and anti-coagulant properties, although the detailed molecular action remains to be elucidated. The aim of the present study is to assess the impact of crude fucoidan extracts, on the formation of vascular structures in co-culture models relevant for bone vascularization during bone repair and for vascularization processes in osteosarcoma. The co-cultures consisted of bone marrow derived mesenchymal stem cells, respectively the osteosarcoma cell line MG63, and human blood derived outgrowth endothelial cells (OEC. The concentration dependent effects on the metabolic activity on endothelial cells and osteoblast cells were first assessed using monocultures of OEC, MSC and MG63 suggesting a concentration of 100 µg/mL as a suitable concentration for further experiments. In co-cultures fucoidan significantly reduced angiogenesis in MSC/OEC but also in MG63/OEC co-cultures suggesting a potential application of fucoidan to lower the vascularization in bone tumors such as osteosarcoma. This was associated with a decrease in VEGF (vascular endothelial growth factor and SDF-1 (stromal derived factor-1 on the protein level, both related to the control of angiogenesis and furthermore discussed as crucial factors in osteosarcoma progression and metastasis. In terms of bone formation, fucoidan slightly lowered on the calcification process in MSC monocultures and MSC/OEC co-cultures. In summary, these data suggest the suitability of lower fucoidan doses to limit angiogenesis for instance in osteosarcoma.

Crude Fucoidan Extracts Impair Angiogenesis in Models Relevant for Bone Regeneration and Osteosarcoma via Reduction of VEGF and SDF-1.

Science.gov (United States)

Wang, Fanlu; Schmidt, Harald; Pavleska, Dijana; Wermann, Thees; Seekamp, Andreas; Fuchs, Sabine

2017-06-20

The marine origin polysaccharide fucoidan combines multiple biological activities. As demonstrated by various studies in vitro and in vivo, fucoidans show anti-viral, anti-tumor, anti-oxidant, anti-inflammatory and anti-coagulant properties, although the detailed molecular action remains to be elucidated. The aim of the present study is to assess the impact of crude fucoidan extracts, on the formation of vascular structures in co-culture models relevant for bone vascularization during bone repair and for vascularization processes in osteosarcoma. The co-cultures consisted of bone marrow derived mesenchymal stem cells, respectively the osteosarcoma cell line MG63, and human blood derived outgrowth endothelial cells (OEC). The concentration dependent effects on the metabolic activity on endothelial cells and osteoblast cells were first assessed using monocultures of OEC, MSC and MG63 suggesting a concentration of 100 µg/mL as a suitable concentration for further experiments. In co-cultures fucoidan significantly reduced angiogenesis in MSC/OEC but also in MG63/OEC co-cultures suggesting a potential application of fucoidan to lower the vascularization in bone tumors such as osteosarcoma. This was associated with a decrease in VEGF (vascular endothelial growth factor) and SDF-1 (stromal derived factor-1) on the protein level, both related to the control of angiogenesis and furthermore discussed as crucial factors in osteosarcoma progression and metastasis. In terms of bone formation, fucoidan slightly lowered on the calcification process in MSC monocultures and MSC/OEC co-cultures. In summary, these data suggest the suitability of lower fucoidan doses to limit angiogenesis for instance in osteosarcoma.

Human Ocular Epithelial Cells Endogenously Expressing SOX2 and OCT4 Yield High Efficiency of Pluripotency Reprogramming.

Directory of Open Access Journals (Sweden)

Ming-Wai Poon

Full Text Available A variety of pluripotency reprogramming frequencies from different somatic cells has been observed, indicating cell origin is a critical contributor for efficiency of pluripotency reprogramming. Identifying the cell sources for efficient induced pluripotent stem cells (iPSCs generation, and defining its advantages or disadvantages on reprogramming, is therefore important. Human ocular tissue-derived conjunctival epithelial cells (OECs exhibited endogenous expression of reprogramming factors OCT4A (the specific OCT 4 isoform on pluripotency reprogramming and SOX2. We therefore determined whether OECs could be used for high efficiency of iPSCs generation. We compared the endogenous expression levels of four pluripotency factors and the pluripotency reprograming efficiency of human OECs with that of ocular stromal cells (OSCs. Real-time PCR, microarray analysis, Western blotting and immunostaining assays were employed to compare OECiPSCs with OSCiPSCs on molecular bases of reprogramming efficiency and preferred lineage-differentiation potential. Using the traditional KMOS (KLF4, C-MYC, OCT4 and SOX2 reprogramming protocol, we confirmed that OECs, endogenously expressing reprogramming factors OCT4A and SOX2, yield very high efficiency of iPSCs generation (~1.5%. Furthermore, higher efficiency of retinal pigmented epithelial differentiation (RPE cells was observed in OECiPSCs compared to OSCiPSCs or skin fibroblast iMR90iPSCs. The findings in this study suggest that conjunctival-derived epithelial (OECs cells can be easier converted to iPSCs than conjunctival-derived stromal cells (OSCs. This cell type may also have advantages in retinal pigmented epithelial differentiation.

Human Ocular Epithelial Cells Endogenously Expressing SOX2 and OCT4 Yield High Efficiency of Pluripotency Reprogramming.

Science.gov (United States)

Poon, Ming-Wai; He, Jia; Fang, Xiaowei; Zhang, Zhao; Wang, Weixin; Wang, Junwen; Qiu, Fangfang; Tse, Hung-Fat; Li, Wei; Liu, Zuguo; Lian, Qizhou

2015-01-01

A variety of pluripotency reprogramming frequencies from different somatic cells has been observed, indicating cell origin is a critical contributor for efficiency of pluripotency reprogramming. Identifying the cell sources for efficient induced pluripotent stem cells (iPSCs) generation, and defining its advantages or disadvantages on reprogramming, is therefore important. Human ocular tissue-derived conjunctival epithelial cells (OECs) exhibited endogenous expression of reprogramming factors OCT4A (the specific OCT 4 isoform on pluripotency reprogramming) and SOX2. We therefore determined whether OECs could be used for high efficiency of iPSCs generation. We compared the endogenous expression levels of four pluripotency factors and the pluripotency reprograming efficiency of human OECs with that of ocular stromal cells (OSCs). Real-time PCR, microarray analysis, Western blotting and immunostaining assays were employed to compare OECiPSCs with OSCiPSCs on molecular bases of reprogramming efficiency and preferred lineage-differentiation potential. Using the traditional KMOS (KLF4, C-MYC, OCT4 and SOX2) reprogramming protocol, we confirmed that OECs, endogenously expressing reprogramming factors OCT4A and SOX2, yield very high efficiency of iPSCs generation (~1.5%). Furthermore, higher efficiency of retinal pigmented epithelial differentiation (RPE cells) was observed in OECiPSCs compared to OSCiPSCs or skin fibroblast iMR90iPSCs. The findings in this study suggest that conjunctival-derived epithelial (OECs) cells can be easier converted to iPSCs than conjunctival-derived stromal cells (OSCs). This cell type may also have advantages in retinal pigmented epithelial differentiation.

'Photosystem II: the water splitting enzyme of photosynthesis and the origin of oxygen in our atmosphere'.

Science.gov (United States)

Barber, James

2016-01-01

inorganic precursor for the evolution of the photosynthetic oxygen-evolving complex. In summary, the overall structure of the catalytic site has given a framework on which to build a mechanistic scheme for photosynthetic dioxygen generation and at the same time provide a blue-print and incentive to develop catalysts for artificial photo-electrochemical systems to split water and generate renewable solar fuels.

Investigations of Trace Oxygenates in Middle Distillate Fuels using Gas Chromatography

OpenAIRE

RENEE LOUISE WEBSTER

2017-01-01

There can be up to one million different compounds in aviation or diesel fuels, making the analysis of trace components within the complex matrix highly challenging. Many trace oxygenated compounds may be present in fuels and can have dramatic effects on the fuel’s properties. Advanced analytical chemistry techniques have been used to contribute a critical understanding of the role of trace oxygenates on the chemistry of both emerging alternate and fossil fuels. Knowledge of these molecular s...

Closed Loop Control of Oxygen Delivery and Oxygen Generation

Science.gov (United States)

2017-08-01

were used for this study and were connected via a USB cable to allow communication. The ventilator was modified to allow closed loop control of oxygen...connected via a USB cable to allow communication. The ventilator was modified to allow closed loop control of oxygen based on the oxygen saturation...2017-4119, 28 Aug 2017. oximetry (SpO2) and intermittent arterial blood sampling for arterial oxygen tension (partial pressure of oxygen [PaO2]) and

Engineering the oxygen coordination in digital superlattices

Science.gov (United States)

Cook, Seyoung; Andersen, Tassie K.; Hong, Hawoong; Rosenberg, Richard A.; Marks, Laurence D.; Fong, Dillon D.

2017-12-01

The oxygen sublattice in complex oxides is typically composed of corner-shared polyhedra, with transition metals at their centers. The electronic and chemical properties of the oxide depend on the type and geometric arrangement of these polyhedra, which can be controlled through epitaxial synthesis. Here, we use oxide molecular beam epitaxy to create SrCoOx:SrTiO3 superlattices with tunable oxygen coordination environments and sublattice geometries. Using synchrotron X-ray scattering in combination with soft X-ray spectroscopy, we find that the chemical state of Co can be varied with the polyhedral arrangement, with higher Co oxidation states increasing the valence band maximum. This work demonstrates a new strategy for engineering unique electronic structures in the transition metal oxides using short-period superlattices.

An Evolving Identity: How Chronic Care Is Transforming What it Means to Be a Physician.

Science.gov (United States)

Bogetz, Alyssa L; Bogetz, Jori F

2015-12-01

Physician identity and the professional role physicians play in health care is rapidly evolving. Over 130 million adults and children in the USA have complex and chronic diseases, each of which is shaped by aspects of the patient's social, psychological, and economic status. These patients have lifelong health care needs that require the ongoing care of multiple health care providers, access to community services, and the involvement of patients' family support networks. To date, physician professional identity formation has centered on autonomy, authority, and the ability to "heal." These notions of identity may be counterproductive in chronic disease care, which demands interdependency between physicians, their patients, and teams of multidisciplinary health care providers. Medical educators can prepare trainees for practice in the current health care environment by providing training that legitimizes and reinforces a professional identity that emphasizes this interdependency. This commentary outlines the important challenges related to this change and suggests potential strategies to reframe professional identity to better match the evolving role of physicians today.

Effects of Hyperoxia on Oxygen-Related Inflammation with a Focus on Obesity

Directory of Open Access Journals (Sweden)

Pedro González-Muniesa

2016-01-01

Full Text Available Several studies have shown a pathological oxygenation (hypoxia/hyperoxia on the adipose tissue in obese subjects. Additionally, the excess of body weight is often accompanied by a state of chronic low-degree inflammation. The inflammation phenomenon is a complex biological response mounted by tissues to combat injurious stimuli in order to maintain cell homeostasis. Furthermore, it is believed that the abnormal oxygen partial pressure occurring in adipose tissue is involved in triggering inflammatory processes. In this context, oxygen is used in modern medicine as a treatment for several diseases with inflammatory components. Thus, hyperbaric oxygenation has demonstrated beneficial effects, apart from improving local tissue oxygenation, on promoting angiogenesis, wound healing, providing neuroprotection, facilitating glucose uptake, appetite, and others. Nevertheless, an excessive hyperoxia exposure can lead to deleterious effects such as oxidative stress, pulmonary edema, and maybe inflammation. Interestingly, some of these favorable outcomes occur under high and low oxygen concentrations. Hereby, we review a potential therapeutic approach to the management of obesity as well as the oxygen-related inflammation accompanying expanded adipose tissue, based on elevated oxygen concentrations. To conclude, we highlight at the end of this review some areas that need further clarification.

The Productivity of Oxygenic Photosynthesis around Cool, M Dwarf Stars

Science.gov (United States)

Lehmer, Owen R.; Catling, David C.; Parenteau, Mary N.; Hoehler, Tori M.

2018-06-01

In the search for life around cool stars, the presence of atmospheric oxygen is a prominent biosignature, as it may indicate oxygenic photosynthesis (OP) on the planetary surface. On Earth, most oxygenic photosynthesizing organisms (OPOs) use photons between 400 and 750 nm, which have sufficient energy to drive the photosynthetic reaction that generates O2 from H2O and CO2. OPOs around cool stars may evolve similar biological machinery capable of producing oxygen from water. However, in the habitable zones (HZs) of the coolest M dwarf stars, the flux of 400–750 nm photons may be just a few percent that of Earth’s. We show that the reduced flux of 400–750 nm photons around M dwarf stars could result in Earth-like planets being growth limited by light, unlike the terrestrial biosphere, which is limited by nutrient availability. We consider stars with photospheric temperatures between 2300 and 4200 K and show that such light-limited worlds could occur at the outer edge of the HZ around TRAPPIST-1-like stars. We find that even if OP can use photons longer than 750 nm, there would still be insufficient energy to sustain the Earth’s extant biosphere throughout the HZ of the coolest stars. This is because such stars emit largely in the infrared and near-infrared, which provide sufficient energy to make the planet habitable, but limits the energy available for OP. TRAPPIST-1f and g may fall into this category. Biospheres on such planets, potentially limited by photon availability, may generate small biogenic signals, which could be difficult for future observations to detect.

Oxygen sensing PLIM together with FLIM of intrinsic cellular fluorophores for metabolic mapping

Science.gov (United States)

Kalinina, Sviatlana; Schaefer, Patrick; Breymayer, Jasmin; Bisinger, Dominik; Chakrabortty, Sabyasachi; Rueck, Angelika

2018-02-01

Otical imaging techniques based on time correlated single photon counting (TCSPC) has found wide applications in medicine and biology. Non-invasive and information-rich fluorescence lifetime imaging microscopy (FLIM) is successfully used for monitoring fluorescent intrinsic metabolic coenzymes as NAD(P)H (nicotinamide adenine dinucleotide (phosphate)) and FAD+ (flavin adenine dinucleotide) in living cells and tissues. The ratio between proteinbound and free coenzymes gives an information about the balance between oxidative phosphorylation and glycolysis in the cells. The changes of the ratio reflects major cellular disorders. A correlation exists between metabolic activity, redox ratio and fluorescence lifetime during stem cell differentiation, neurodegenerative diseases, and carcinogenesis. A multichannel FLIM detection system was designed for monitoring the redox state of NAD(P)H and FAD+ and other intrinsic fluorophores as protoporphyrin IX. In addition, the unique upgrade is useful to perform FLIM and PLIM (phosphorescence lifetime imaging microscopy) simultaneously. PLIM is a promising method to investigate oxygen sensing in biomedical samples. In detail, the oxygen-dependent quenching of phosphorescence of some compounds as transition metal complexes enables measuring of oxygen partial pressure (pO2). Using a two-channel FLIM/PLIM system we monitored intrinsic pO2 by PLIM simultaneously with NAD(P)H by FLIM providing complex metabolic and redox imaging of living cells. Physico-chemical properties of oxygen sensitive probes define certain parameters including their localisation. We present results of some ruthenium based complexes including those specifically bound to mitochondria.

Evolving Procurement Organizations

DEFF Research Database (Denmark)

Bals, Lydia; Laine, Jari; Mugurusi, Godfrey

Procurement has to find further levers and advance its contribution to corporate goals continuously. This places pressure on its organization in order to facilitate its performance. Therefore, procurement organizations constantly have to evolve in order to match these demands. A conceptual model...... and external contingency factors and having a more detailed look at the structural dimensions chosen, beyond the well-known characteristics of centralization, formalization, participation, specialization, standardization and size. From a theoretical perspective, it opens up insights that can be leveraged...

High-Energy-Density Metal-Oxygen Batteries: Lithium-Oxygen Batteries vs Sodium-Oxygen Batteries.

Science.gov (United States)

Song, Kyeongse; Agyeman, Daniel Adjei; Park, Mihui; Yang, Junghoon; Kang, Yong-Mook

2017-12-01

The development of next-generation energy-storage devices with high power, high energy density, and safety is critical for the success of large-scale energy-storage systems (ESSs), such as electric vehicles. Rechargeable sodium-oxygen (Na-O 2 ) batteries offer a new and promising opportunity for low-cost, high-energy-density, and relatively efficient electrochemical systems. Although the specific energy density of the Na-O 2 battery is lower than that of the lithium-oxygen (Li-O 2 ) battery, the abundance and low cost of sodium resources offer major advantages for its practical application in the near future. However, little has so far been reported regarding the cell chemistry, to explain the rate-limiting parameters and the corresponding low round-trip efficiency and cycle degradation. Consequently, an elucidation of the reaction mechanism is needed for both lithium-oxygen and sodium-oxygen cells. An in-depth understanding of the differences and similarities between Li-O 2 and Na-O 2 battery systems, in terms of thermodynamics and a structural viewpoint, will be meaningful to promote the development of advanced metal-oxygen batteries. State-of-the-art battery design principles for high-energy-density lithium-oxygen and sodium-oxygen batteries are thus reviewed in depth here. Major drawbacks, reaction mechanisms, and recent strategies to improve performance are also summarized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laplacian Estrada and normalized Laplacian Estrada indices of evolving graphs.

Science.gov (United States)

Shang, Yilun

2015-01-01

Large-scale time-evolving networks have been generated by many natural and technological applications, posing challenges for computation and modeling. Thus, it is of theoretical and practical significance to probe mathematical tools tailored for evolving networks. In this paper, on top of the dynamic Estrada index, we study the dynamic Laplacian Estrada index and the dynamic normalized Laplacian Estrada index of evolving graphs. Using linear algebra techniques, we established general upper and lower bounds for these graph-spectrum-based invariants through a couple of intuitive graph-theoretic measures, including the number of vertices or edges. Synthetic random evolving small-world networks are employed to show the relevance of the proposed dynamic Estrada indices. It is found that neither the static snapshot graphs nor the aggregated graph can approximate the evolving graph itself, indicating the fundamental difference between the static and dynamic Estrada indices.

Imprint and oxygen deficiency in (Pb,La)(Zr,Ti)O3 thin-film capacitors with La-Sr-Co-O electrodes

International Nuclear Information System (INIS)

Lee, J.; Ramesh, R.; Keramidas, V.G.; Warren, W.L.; Pike, G.E.; Evans, J.T. Jr.

1995-01-01

La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O thin-film capacitors have been grown in various oxygen ambients by pulsed laser deposition. As the oxygen ambient became more reducing, the capacitors developed more voltage asymmetry in hysteresis loops and a more preferred polarization state directed towards the top electrode. PLZT capacitors cooled in a fully oxidizing atmosphere (i.e., 1 atm oxygen pressure) exhibited nominally symmetric hysteresis loops and also showed little imprint both with and without fully saturating bias fields. We find that ambient oxygen pressure is an important process parameter and the imprint behavior is closely related with ambient oxygen induced effects such as oxygen vacancies, its related defect-dipole complexes and trapping of free charges. The different imprint behavior under negative and positive bias also suggests that the dipolar-defect complexes tend to cause imprint in PLZT capacitors

Oxygen Therapy

Directory of Open Access Journals (Sweden)

Bonnie Solmes

2000-01-01

Full Text Available LTOT is prescribed for people with chronic lung disease in whom there is a decrease in the ability of the lungs to supply enough oxygen to the body. The heart is obliged to pump faster to meet the body's oxygen requirements. This may place undue stress on the heart, resulting in palpitations, dizziness and fatigue. A low oxygen level in arterial blood is also harmful to the heart, the brain and the pulmonary blood vessels. Oxygen therapy is used to break this cycle. A person with low blood oxygen will often be able to accomplish more with less fatigue with the help of supplemental oxygen therapy. Shortness of breath is a mechanical problem resulting from the effects of chronic obstructive pulmonary disease. Oxygen therapy may or may not reduce shortness of breath, but it will help the lungs and heart to function with less stress.

Evolution of complexity in RNA-like replicator systems

Directory of Open Access Journals (Sweden)

Hogeweg Paulien

2008-03-01

Full Text Available Abstract Background The evolution of complexity is among the most important questions in biology. The evolution of complexity is often observed as the increase of genetic information or that of the organizational complexity of a system. It is well recognized that the formation of biological organization – be it of molecules or ecosystems – is ultimately instructed by the genetic information, whereas it is also true that the genetic information is functional only in the context of the organization. Therefore, to obtain a more complete picture of the evolution of complexity, we must study the evolution of both information and organization. Results Here we investigate the evolution of complexity in a simulated RNA-like replicator system. The simplicity of the system allows us to explicitly model the genotype-phenotype-interaction mapping of individual replicators, whereby we avoid preconceiving the functionality of genotypes (information or the ecological organization of replicators in the model. In particular, the model assumes that interactions among replicators – to replicate or to be replicated – depend on their secondary structures and base-pair matching. The results showed that a population of replicators, originally consisting of one genotype, evolves to form a complex ecosystem of up to four species. During this diversification, the species evolve through acquiring unique genotypes with distinct ecological functionality. The analysis of this diversification reveals that parasitic replicators, which have been thought to destabilize the replicator's diversity, actually promote the evolution of diversity through generating a novel "niche" for catalytic replicators. This also makes the current replicator system extremely stable upon the evolution of parasites. The results also show that the stability of the system crucially depends on the spatial pattern formation of replicators. Finally, the evolutionary dynamics is shown to

Modeling the oxygen microheterogeneity of tumors for photodynamic therapy dosimetry

Science.gov (United States)

Pogue, Brian W.; Paulsen, Keith D.; O'Hara, Julia A.; Hoopes, P. Jack; Swartz, Harold

2000-03-01

Photodynamic theory of tumors uses optical excitation of a sensitizing drug within tissue to produce large deposits of singlet oxygen, which are thought to ultimately cause the tumor destruction. Predicting dose deposition of singlet oxygen in vivo is challenging because measurement of this species in vivo is not easily achieved. But it is possible to follow the concentration of oxygen in vivo, and so measuring the oxygen concentration transients during PDT may provide a viable method of estimating the delivered dose of singlet oxygen. However modeling the microscopic heterogeneity of the oxygen distribution within a tumor is non-trivial, and predicting the microscopic dose deposition requires further study, but this study present the framework and initial calibration needed or modeling oxygen transport in complex geometries. Computational modeling with finite elements provides a versatile structure within which oxygen diffusion and consumption can be modeled within realistic tissue geometries. This study develops the basic tools required to simulate a tumor region, and examines the role of (i) oxygen supply and consumption rates, (ii) inter- capillary spacing, (iii) photosensitizer distribution, and (iv) differences between simulated tumors and those derived directly from histology. The result of these calculations indicate that realistic tumor tissue capillary networks can be simulated using the finite element method, without excessive computational burden for 2D regions near 1 mm2, and 3D regions near 0.1mm3. These simulations can provide fundamental information about tissue and ways to implement appropriate oxygen measurements. These calculations suggest that photodynamic therapy produces the majority of singlet oxygen in and near the blood vessels, because these are the sites of highest oxygen tension. These calculations support the concept that tumor vascular regions are the major targets for PDT dose deposition.

[Domiciliary oxygen therapy].

Science.gov (United States)

Abdel Kafi, S

2010-09-01

In Belgium, oxygen therapy is becoming more and more accessible. When oxygen is needed for short periods or for special indications as palliative care, an agreement between mutual insurance companies and pharmacists allows the practitioner the home installation of gazeous oxygen cylinder or of oxygen concentrator. When long term oxygen therapy (LTOT) is indicated for patients with respiratory insufficiency, the pneumologist must first ask the INAMI the authorization to install one of the following modalities: oxygen concentrator with or without demand oxygen delivery cylinder and liquid oxygen. The goal of LTOT is to increase survival and quality of life. The principal and well accepted indication for LTOT is severe hypoxemia. The beneficial effects of oxygen therapy limited at night or on exertion are controversial. In order to increase patient's autonomy, oxygen can be prescribed for ambulation, respecting prescription's rules. At each step of oxygen therapy implementing (indication, choice of the device and follow-up) the patient under oxygen may benefit from a joint approach between the general practitioner and the chest specialist.

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Science.gov (United States)

Pan, Zhong-Hua; Tao, Yun-Wen; He, Quan-Feng; Wu, Qiao-Yu; Cheng, Li-Ping; Wei, Zhan-Hua; Wu, Ji-Huai; Lin, Jin-Qing; Sun, Di; Zhang, Qi-Chun; Tian, Dan; Luo, Geng-Geng

2018-06-12

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H 2 evolution turnover frequency (TOF) of 7838 s -1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s -1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H 2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O 2 and H 2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolvable Smartphone-Based Platforms for Point-of-Care In-Vitro Diagnostics Applications

Science.gov (United States)

Patou, François; AlZahra’a Alatraktchi, Fatima; Kjægaard, Claus; Dimaki, Maria; Madsen, Jan; Svendsen, Winnie E.

2016-01-01

The association of smart mobile devices and lab-on-chip technologies offers unprecedented opportunities for the emergence of direct-to-consumer in vitro medical diagnostics applications. Despite their clear transformative potential, obstacles remain to the large-scale disruption and long-lasting success of these systems in the consumer market. For instance, the increasing level of complexity of instrumented lab-on-chip devices, coupled to the sporadic nature of point-of-care testing, threatens the viability of a business model mainly relying on disposable/consumable lab-on-chips. We argued recently that system evolvability, defined as the design characteristic that facilitates more manageable transitions between system generations via the modification of an inherited design, can help remedy these limitations. In this paper, we discuss how platform-based design can constitute a formal entry point to the design and implementation of evolvable smart device/lab-on-chip systems. We present both a hardware/software design framework and the implementation details of a platform prototype enabling at this stage the interfacing of several lab-on-chip variants relying on current- or impedance-based biosensors. Our findings suggest that several change-enabling mechanisms implemented in the higher abstraction software layers of the system can promote evolvability, together with the design of change-absorbing hardware/software interfaces. Our platform architecture is based on a mobile software application programming interface coupled to a modular hardware accessory. It allows the specification of lab-on-chip operation and post-analytic functions at the mobile software layer. We demonstrate its potential by operating a simple lab-on-chip to carry out the detection of dopamine using various electroanalytical methods. PMID:27598208

Evolvable Smartphone-Based Platforms for Point-of-Care In-Vitro Diagnostics Applications.

Science.gov (United States)

Patou, François; AlZahra'a Alatraktchi, Fatima; Kjægaard, Claus; Dimaki, Maria; Madsen, Jan; Svendsen, Winnie E

2016-09-03

The association of smart mobile devices and lab-on-chip technologies offers unprecedented opportunities for the emergence of direct-to-consumer in vitro medical diagnostics applications. Despite their clear transformative potential, obstacles remain to the large-scale disruption and long-lasting success of these systems in the consumer market. For instance, the increasing level of complexity of instrumented lab-on-chip devices, coupled to the sporadic nature of point-of-care testing, threatens the viability of a business model mainly relying on disposable/consumable lab-on-chips. We argued recently that system evolvability, defined as the design characteristic that facilitates more manageable transitions between system generations via the modification of an inherited design, can help remedy these limitations. In this paper, we discuss how platform-based design can constitute a formal entry point to the design and implementation of evolvable smart device/lab-on-chip systems. We present both a hardware/software design framework and the implementation details of a platform prototype enabling at this stage the interfacing of several lab-on-chip variants relying on current- or impedance-based biosensors. Our findings suggest that several change-enabling mechanisms implemented in the higher abstraction software layers of the system can promote evolvability, together with the design of change-absorbing hardware/software interfaces. Our platform architecture is based on a mobile software application programming interface coupled to a modular hardware accessory. It allows the specification of lab-on-chip operation and post-analytic functions at the mobile software layer. We demonstrate its potential by operating a simple lab-on-chip to carry out the detection of dopamine using various electroanalytical methods.

Evolvable Smartphone-Based Platforms for Point-of-Care In-Vitro Diagnostics Applications

Directory of Open Access Journals (Sweden)

François Patou

2016-09-01

Full Text Available The association of smart mobile devices and lab-on-chip technologies offers unprecedented opportunities for the emergence of direct-to-consumer in vitro medical diagnostics applications. Despite their clear transformative potential, obstacles remain to the large-scale disruption and long-lasting success of these systems in the consumer market. For instance, the increasing level of complexity of instrumented lab-on-chip devices, coupled to the sporadic nature of point-of-care testing, threatens the viability of a business model mainly relying on disposable/consumable lab-on-chips. We argued recently that system evolvability, defined as the design characteristic that facilitates more manageable transitions between system generations via the modification of an inherited design, can help remedy these limitations. In this paper, we discuss how platform-based design can constitute a formal entry point to the design and implementation of evolvable smart device/lab-on-chip systems. We present both a hardware/software design framework and the implementation details of a platform prototype enabling at this stage the interfacing of several lab-on-chip variants relying on current- or impedance-based biosensors. Our findings suggest that several change-enabling mechanisms implemented in the higher abstraction software layers of the system can promote evolvability, together with the design of change-absorbing hardware/software interfaces. Our platform architecture is based on a mobile software application programming interface coupled to a modular hardware accessory. It allows the specification of lab-on-chip operation and post-analytic functions at the mobile software layer. We demonstrate its potential by operating a simple lab-on-chip to carry out the detection of dopamine using various electroanalytical methods.

Celastrol targets mitochondrial respiratory chain complex I to induce reactive oxygen species-dependent cytotoxicity in tumor cells

Directory of Open Access Journals (Sweden)

Xu Yuanji

2011-05-01

Full Text Available Abstract Background Celastrol is an active ingredient of the traditional Chinese medicinal plant Tripterygium Wilfordii, which exhibits significant antitumor activity in different cancer models in vitro and in vivo; however, the lack of information on the target and mechanism of action of this compound have impeded its clinical application. In this study, we sought to determine the mode of action of celastrol by focusing on the processes that mediate its anticancer activity. Methods The downregulation of heat shock protein 90 (HSP90 client proteins, phosphorylation of c-Jun NH2-terminal kinase (JNK, and cleavage of PARP, caspase 9 and caspase 3 were detected by western blotting. The accumulation of reactive oxygen species (ROS was analyzed by flow cytometry and fluorescence microscopy. Cell cycle progression, mitochondrial membrane potential (MMP and apoptosis were determined by flow cytometry. Absorption spectroscopy was used to determine the activity of mitochondrial respiratory chain (MRC complexes. Results Celastrol induced ROS accumulation, G2-M phase blockage, apoptosis and necrosis in H1299 and HepG2 cells in a dose-dependent manner. N-acetylcysteine (NAC, an antioxidative agent, inhibited celastrol-induced ROS accumulation and cytotoxicity. JNK phosphorylation induced by celastrol was suppressed by NAC and JNK inhibitor SP600125 (SP. Moreover, SP significantly inhibited celastrol-induced loss of MMP, cleavage of PARP, caspase 9 and caspase 3, mitochondrial translocation of Bad, cytoplasmic release of cytochrome c, and cell death. However, SP did not inhibit celastrol-induced ROS accumulation. Celastrol downregulated HSP90 client proteins but did not disrupt the interaction between HSP90 and cdc37. NAC completely inhibited celastrol-induced decrease of HSP90 client proteins, catalase and thioredoxin. The activity of MRC complex I was completely inhibited in H1299 cells treated with 6 μM celastrol in the absence and presence of NAC

Oxygen therapy - infants

Science.gov (United States)

... breathe increased amounts of oxygen to get normal levels of oxygen in their blood. Oxygen therapy provides babies with the extra oxygen. Information Oxygen is a gas that the cells in your body need to work properly. The ...

bond activation and catalysis by Ru -pac complexes

Indian Academy of Sciences (India)

and their reactivity towards oxidation of a few organic compounds. Keywords. Kinetics; catalysis; -O–O- bond activation; Ru-pac complex; oxidation. 1. Introduction. Ru-pac complexes exhibit catalytic properties,1 in homogeneous conditions in the presence of oxygen atom donors, that mimic the biological enzymatic oxi-.

From precision polymers to complex materials and systems

NARCIS (Netherlands)

Lutz, J.F.; Lehn, J.M.; Meijer, E.W.; Matyjaszewski, K.

2016-01-01

Complex chemical systems, such as living biological matter, are highly organized structures based on discrete molecules in constant dynamic interactions. These natural materials can evolve and adapt to their environment. By contrast, man-made materials exhibit simpler properties. In this Review, we

Molecular complexes of tungsten oxotetrachloride with azomethins

International Nuclear Information System (INIS)

Abramenko, Yu.V.; Garnovskij, A.D.; Abramenko, V.A.; Medvedeva, T.E.

1992-01-01

Series of new molecular complexes of tungsten oxotetrachloride with benza- and salicylalimines of equimolar compositions obtained. Substances are studied using element analysis, IR spectroscopy and conductometry. Octahedral structure of complexes with central atom coordination of benzalaniline molecules via azomethin nitrogen atom, and salicylalimines - via carbonyl oxygen atom of quinoid tantometric form of ligand is assumed

Factors in the complexation of lanthanides

International Nuclear Information System (INIS)

Choppin, G.R.

1976-01-01

The lanthanide cations are classified as hard acids and thus will coordinate strongly with oxygen and fluorine donor atoms. The electrostatic model is applied to lanthanide complexes with the dielectric constant as a parameter; the plot of ΔG vs sum of ionic radii confirm the ionic nature of the bonding. The enthalpy and entropy changes are shown to compensate each other to produce an almost linear variation in the free energy of complexation. Outer-sphere and inner-sphere complexation is discussed

Laplacian Estrada and normalized Laplacian Estrada indices of evolving graphs.

Directory of Open Access Journals (Sweden)

Yilun Shang

Full Text Available Large-scale time-evolving networks have been generated by many natural and technological applications, posing challenges for computation and modeling. Thus, it is of theoretical and practical significance to probe mathematical tools tailored for evolving networks. In this paper, on top of the dynamic Estrada index, we study the dynamic Laplacian Estrada index and the dynamic normalized Laplacian Estrada index of evolving graphs. Using linear algebra techniques, we established general upper and lower bounds for these graph-spectrum-based invariants through a couple of intuitive graph-theoretic measures, including the number of vertices or edges. Synthetic random evolving small-world networks are employed to show the relevance of the proposed dynamic Estrada indices. It is found that neither the static snapshot graphs nor the aggregated graph can approximate the evolving graph itself, indicating the fundamental difference between the static and dynamic Estrada indices.

Do metaphors evolve? The case of the social organism

DEFF Research Database (Denmark)

Mouton, Nicolaas T.O.

2013-01-01

A long line of philosophers and social scientists have defended and extended the curious idea that collective entities – states and societies, cities and corporations – are biological organisms. In this article, I study a few short but spectacular episodes from the history of that metaphor......, juxtapose mappings made in one era with correspondences conjured in other epochs, and reflect upon the reasons why they differ. By adopting a historical perspective on the process whereby the notion of a “social organism” evolved from its relatively simple beginnings in ancient philosophy to its rather...... complex manifestations in the modern social sciences, I hope to show that there are good reasons to reconsider both Lakoff’s decree that metaphors “should not be thought of as processes”, and his declaration that they should instead be seen as consisting of “a fixed pattern of ontological correspondences...

A distributed chemosensory circuit for oxygen preference in C. elegans.

Directory of Open Access Journals (Sweden)

Andy J Chang

2006-09-01

Full Text Available The nematode Caenorhabditis elegans has complex, naturally variable behavioral responses to environmental oxygen, food, and other animals. C. elegans detects oxygen through soluble guanylate cyclase homologs (sGCs and responds to it differently depending on the activity of the neuropeptide receptor NPR-1: npr-1(lf and naturally isolated npr-1(215F animals avoid high oxygen and aggregate in the presence of food; npr-1(215V animals do not. We show here that hyperoxia avoidance integrates food with npr-1 activity through neuromodulation of a distributed oxygen-sensing network. Hyperoxia avoidance is stimulated by sGC-expressing oxygen-sensing neurons, nociceptive neurons, and ADF sensory neurons. In npr-1(215V animals, the switch from weak aerotaxis on food to strong aerotaxis in its absence requires close regulation of the neurotransmitter serotonin in the ADF neurons; high levels of ADF serotonin promote hyperoxia avoidance. In npr-1(lf animals, food regulation is masked by increased activity of the oxygen-sensing neurons. Hyperoxia avoidance is also regulated by the neuronal TGF-beta homolog DAF-7, a secreted mediator of crowding and stress responses. DAF-7 inhibits serotonin synthesis in ADF, suggesting that ADF serotonin is a convergence point for regulation of hyperoxia avoidance. Coalitions of neurons that promote and repress hyperoxia avoidance generate a subtle and flexible response to environmental oxygen.

Evidence of sub-10 nm aluminum-oxygen precipitates in silicon

International Nuclear Information System (INIS)

Moutanabbir, Oussama; Isheim, Dieter; Mao, Zugang; Seidman, David N

2016-01-01

In this research, ultraviolet laser-assisted atom-probe tomography (APT) was utilized to investigate precisely the behavior at the atomistic level of aluminum impurities in ultrathin epitaxial silicon layers. Aluminum atoms were incorporated in situ during the growth process. The measured average aluminum concentration in the grown layers exceeds by several orders of magnitude the equilibrium bulk solubility. Three-dimensional atom-by-atom mapping demonstrates that aluminum atoms precipitate in the silicon matrix and form nanoscopic precipitates with lateral dimensions in the 1.3 to 6.2 nm range. These precipitates were found to form only in the presence of oxygen impurity atoms, thus providing clear evidence of the long-hypothesized role of oxygen and aluminum-oxygen complexes in facilitating the precipitation of aluminum in a silicon lattice. The measured average aluminum and oxygen concentrations in the precipitates are ∼10 ± 0.5 at.% and ∼4.4 ± 0.5 at.%, respectively. This synergistic interaction is supported by first-principles calculations of the binding energies of aluminum-oxygen dimers in silicon. The calculations demonstrate that there is a strong binding between aluminum and oxygen atoms, with Al-O-Al and O-Al-Al as the energetically favorable sequences corresponding to precipitates in which the concentration of aluminum is twice as large as the oxygen concentration in agreement with APT data. (paper)