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Sample records for barrier oxidation dependence

  1. Effect of oxide barrier height in spin dependent tunneling in MTJ of FeO-MgO multilayer structure

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, M.; Nemade, H.; Bandyopadhyay, D.

    2016-10-01

    We study the spin dependent tunneling current properties through oxide multilayers in a magnetic tunnel junction (MTJ). For this purpose, nonequilibrium Green's function approach along-with the density-functional theory have been applied. We employed three structural models of FeO-MgO-FeO multi-layer with three different width of FeO and MgO layer. An atomistic model is considered to describe the effect of oxide multilayers of different heights. Spin dependent study for tunneling reveals that the parallel spin shows higher tunneling current whereas anti-parallel spin conducts very less. Further, the lowest tunneling current is obtained for the case where the FeO and MgO each has 3 atomic layers of height whereas the tunneling current is highest in 4 atomic layers of FeO/1 atomic layers of MgO/4 atomic layers of MgO multilayer structure. Importantly, when the MgO or FeO layers are increased or decreased from this level, the tunneling current decreases significantly. The study reveals that the layer height in the tunneling domain can be important factor for tuning and adjusting tunneling current in the nanoscale regime of oxide layer thickness.

  2. Lung endothelial barrier protection by resveratrol involves inhibition of HMGB1 release and HMGB1-induced mitochondrial oxidative damage via an Nrf2-dependent mechanism.

    PubMed

    Dong, Wen-Wen; Liu, Yu-Jian; Lv, Zhou; Mao, Yan-Fei; Wang, Ying-Wei; Zhu, Xiao-Yan; Jiang, Lai

    2015-11-01

    High-mobility group box 1 (HMGB1) contributes to lung vascular hyperpermeability during ventilator-induced lung injury. We aimed to determine whether the natural antioxidant resveratrol protected against HMGB1-induced endothelial hyperpermeability both in vitro and in vivo. We found that HMGB1 decreased vascular endothelial (VE)-cadherin expression and increased endothelial permeability, leading to mitochondrial oxidative damage in primary cultured mouse lung vascular endothelial cells (MLVECs). Both the mitochondrial superoxide dismutase 2 mimetic MnTBAP and resveratrol blocked HMGB1-induced mitochondrial oxidative damage, VE-cadherin downregulation, and endothelial hyperpermeability. In in vivo studies, anesthetized male ICR mice were ventilated for 4h using low tidal volume (6 ml/kg) or high tidal volume (HVT; 30 ml/kg) ventilation. The mice were injected intraperitoneally with resveratrol immediately before the onset of ventilation. We found that resveratrol attenuated HVT-associated lung vascular hyperpermeability and HMGB1 production. HVT caused a significant increase in nuclear factor-erythroid 2-related factor 2 (Nrf2) nuclear translocation and Nrf2 target gene expression in lung tissues, which was further enhanced by resveratrol treatment. HMGB1 had no effect on Nrf2 activation, whereas resveratrol treatment activated the Nrf2 signaling pathway in HMGB1-treated MLVECs. Moreover, Nrf2 knockdown reversed the inhibitory effects of resveratrol on HMGB1-induced mitochondrial oxidative damage and endothelial hyperpermeability. The inhibitory effect of resveratrol on cyclic stretch-induced HMGB1 mRNA expression in primary cultured MLVECs was also abolished by Nrf2 knockdown. In summary, this study demonstrates that resveratrol protects against lung endothelial barrier dysfunction initiated by HVT. Lung endothelial barrier protection by resveratrol involves inhibition of mechanical stretch-induced HMGB1 release and HMGB1-induced mitochondrial oxidative damage

  3. The formation mechanism of aluminum oxide tunnel barriers.

    SciTech Connect

    Cerezo, A.; Petford-Long, A. K.; Larson, D. J.; Pinitsoontorn, S.; Singleton, E. W.; Materials Science Division; Univ. Oxford; Seagate Tech.

    2006-01-01

    The functional properties of magnetic tunnel junctions are critically dependant on the nanoscale morphology of the insulating barrier (usually only a few atomic layers thick) that separates the two ferromagnetic layers. Three-dimensional atom probe analysis has been used to study the chemistry of a magnetic tunnel junction structure comprising an aluminium oxide barrier formed by in situ oxidation, both in the under-oxidized and fully oxidized states and before and after annealing. Low oxidation times result in discrete oxide islands. Further oxidation leads to a more continuous, but still non-stoichiometric, barrier with evidence that oxidation proceeds along the top of grain boundaries in the underlying CoFe layer. Post-deposition annealing leads to an increase in the barrier area, but only in the case of the fully oxidized and annealed structure is a continuous planar layer formed, which is close to the stoichiometric Al:O ratio of 2:3. These results are surprising, in that the planar layers are usually considered unstable with respect to breaking up into separate islands. Analysis of the various driving forces suggests that the formation of a continuous layer requires a combination of factors, including the strain energy resulting from the expansion of the oxide during internal oxidation on annealing.

  4. Spin-dependent tunnel junctions with ZrOx barriers

    NASA Astrophysics Data System (ADS)

    Wang, Jianguo; Freitas, P. P.; Snoeck, E.; Wei, P.; Soares, J. C.

    2001-12-01

    Spin-dependent tunnel junctions with crystalline ZrOx barriers were fabricated, with tunnel magnetoresistance (TMR) reaching 20% and a resistance×area product of 24 k Ω μm2, after annealing at 260 °C. Effective barrier height and thickness are 1.6 eV and 10.6 Å, respectively. The ZrOx barriers were fabricated by rf plasma oxidation of a 5 Å thick Zr layer. High-resolution transmission electron microscopy and Rutherford backscattering spectrometry were used to characterize the as-deposited barrier. Both ZrO and ZrO2 phases are present, together with (CoFe)Ox. Upon annealing, the interfacial oxygen moves into the barrier, resulting in an increase of TMR from 2% to 19.2%, an increase of barrier height from 0.3 to 1.6 eV, and a reduction of barrier thickness from 18.5 to 10.5 Å.

  5. Graphene tunnel junctions with aluminum oxide barrier

    NASA Astrophysics Data System (ADS)

    Feng, Ying; Trainer, Daniel J.; Chen, Ke

    2016-10-01

    We report a development of graphene tunnel junctions made by chemical vapor deposition grown graphene and sputtered aluminum insulating by an in-situ grown aluminum oxide. The thin oxide layer formed in between the metal layer and the two-dimensional material is a crucial part of a tunnel junction. We characterized surface morphology of oxide layers and studied tunneling spectra of lead and silver tunnel junctions to estimate the quality of the aluminum oxide. The Brinkman-Rowell-Dynes model was applied to fit the conductance-voltage plots to calculate the thickness of oxide layers. Junctions with graphene both on bottom and on top were fabricated and their tunneling properties were characterized after exposure to air for weeks to test time stability. Furthermore, the resistances of graphene tunnel junctions with aluminum oxide formed naturally and in an oxygen atmosphere were studied. Our results demonstrate that in-situ aluminum oxide is an effective barrier for graphene tunnel junctions. The methods of barrier formation enable the realization of more tunnel devices and circuits based on graphene.

  6. Moderate Hypoxia Followed by Reoxygenation Results in Blood-Brain Barrier Breakdown via Oxidative Stress-Dependent Tight-Junction Protein Disruption

    PubMed Central

    Zehendner, Christoph M.; Librizzi, Laura; Hedrich, Jana; Bauer, Nina M.; Angamo, Eskedar A.; de Curtis, Marco; Luhmann, Heiko J.

    2013-01-01

    Re-canalization of cerebral vessels in ischemic stroke is pivotal to rescue dysfunctional brain areas that are exposed to moderate hypoxia within the penumbra from irreversible cell death. Goal of the present study was to evaluate the effect of moderate hypoxia followed by reoxygenation (MHR) on the evolution of reactive oxygen species (ROS) and blood-brain barrier (BBB) integrity in brain endothelial cells (BEC). BBB integrity was assessed in BEC in vitro and in microvessels of the guinea pig whole brain in situ preparation. Probes were exposed to MHR (2 hours 67-70 mmHg O2, 3 hours reoxygenation, BEC) or towards occlusion of the arteria cerebri media (MCAO) with or without subsequent reperfusion in the whole brain preparation. In vitro BBB integrity was evaluated using trans-endothelial electrical resistance (TEER) and transwell permeability assays. ROS in BEC were evaluated using 2′,7′-dichlorodihydrofluorescein diacetate (DCF), MitoSox and immunostaining for nitrotyrosine. Tight-junction protein (TJ) integrity in BEC, stainings for nitrotyrosine and FITC-albumin extravasation in the guinea pig brain preparation were assessed by confocal microscopy. Diphenyleneiodonium (DPI) was used to investigate NADPH oxidase dependent ROS evolution and its effect on BBB parameters in BEC. MHR impaired TJ proteins zonula occludens 1 (ZO-1) and claudin 5 (Cl5), decreased TEER, and significantly increased cytosolic ROS in BEC. These events were blocked by the NADPH oxidase inhibitor DPI. MCAO with or without subsequent reoxygenation resulted in extravasation of FITC-albumin and ROS generation in the penumbra region of the guinea pig brain preparation and confirmed BBB damage. BEC integrity may be impaired through ROS in MHR on the level of TJ and the BBB is also functionally impaired in moderate hypoxic conditions followed by reperfusion in a complex guinea pig brain preparation. These findings suggest that the BBB is susceptible towards MHR and that ROS play a key role in

  7. Signalling of DNA damage and cytokines across cell barriers exposed to nanoparticles depends on barrier thickness

    NASA Astrophysics Data System (ADS)

    Sood, A.; Salih, S.; Roh, D.; Lacharme-Lora, L.; Parry, M.; Hardiman, B.; Keehan, R.; Grummer, R.; Winterhager, E.; Gokhale, P. J.; Andrews, P. W.; Abbott, C.; Forbes, K.; Westwood, M.; Aplin, J. D.; Ingham, E.; Papageorgiou, I.; Berry, M.; Liu, J.; Dick, A. D.; Garland, R. J.; Williams, N.; Singh, R.; Simon, A. K.; Lewis, M.; Ham, J.; Roger, L.; Baird, D. M.; Crompton, L. A.; Caldwell, M. A.; Swalwell, H.; Birch-Machin, M.; Lopez-Castejon, G.; Randall, A.; Lin, H.; Suleiman, M.-S.; Evans, W. H.; Newson, R.; Case, C. P.

    2011-12-01

    The use of nanoparticles in medicine is ever increasing, and it is important to understand their targeted and non-targeted effects. We have previously shown that nanoparticles can cause DNA damage to cells cultured below a cellular barrier without crossing this barrier. Here, we show that this indirect DNA damage depends on the thickness of the cellular barrier, and it is mediated by signalling through gap junction proteins following the generation of mitochondrial free radicals. Indirect damage was seen across both trophoblast and corneal barriers. Signalling, including cytokine release, occurred only across bilayer and multilayer barriers, but not across monolayer barriers. Indirect toxicity was also observed in mice and using ex vivo explants of the human placenta. If the importance of barrier thickness in signalling is a general feature for all types of barriers, our results may offer a principle with which to limit the adverse effects of nanoparticle exposure and offer new therapeutic approaches.

  8. Diffusion Barriers to Increase the Oxidative Life of Overlay Coatings

    NASA Technical Reports Server (NTRS)

    Nesbitt, James A.; Lei, Jih-Fen

    1999-01-01

    Currently, most blades and vanes in the hottest section of aero gas turbine engines require some type of coating for oxidation protection. Newly developed single crystal superalloys have the mechanical potential to operate at increasingly higher component temperatures. However, at these elevated temperatures, coating/substrate interdiffusion can shorten the protective life of the coating. Diffusion barriers between overlay coatings and substrates are being examined to extend the protective life of the coating. A previously- developed finite-difference diffusion model has been modified to predict the oxidative life enhancement due to use of a diffusion barrier. The original diffusion model, designated COSIM, simulates Al diffusion in the coating to the growing oxide scale as well as Al diffusion into the substrate. The COSIM model incorporates an oxide growth and spalling model to provide the rate of Al consumption during cyclic oxidation. Coating failure is predicted when the Al concentration at the coating surface drops to a defined critical level. The modified COSIM model predicts the oxidative life of an overlay coating when a diffusion barrier is present eliminating diffusion of Al from the coating into the substrate. Both the original and the modified diffusion models have been used to predict the effectiveness of a diffusion barrier in extending the protective life of a NiCrAl overlay coating undergoing cyclic oxidation at 1100 C.

  9. Oxidation of tunnel barrier metals in magnetic tunnel junctions

    NASA Astrophysics Data System (ADS)

    Yang, J. Joshua; Ladwig, Peter F.; Yang, Ying; Ji, Chengxiang; Chang, Y. Austin; Liu, Feng X.; Pant, Bharat B.; Schultz, Allan E.

    2005-05-01

    The oxidation of an ultrathin metal layer (<1nm) to form an oxide tunnel barrier is of critical importance for the fabrication of magnetic tunnel junctions (MTJs) with low product of resistance and area (R×A). Nonuniform and excessive or insufficient oxidation will occur by using conventional plasma, air, or O2 and noble gas mixtures as oxidation methods. An oxidation method was investigated to oxidize only an ultrathin layer of metal (such as Y) without oxidizing adjacent ferromagnetic thin film layers. We have now demonstrated that a gas mixture of H2O/H2 with a fixed chemical potential of oxygen determined by the relative amounts of the two gases can oxidize Y and Ta thin layers while simultaneously keeping a Co ferromagnetic layer completely unoxidized. This universal method can be used to preferentially oxidize a host of other metals with high tendency to form oxides, such as Zr, Hf, Nb, rare earth metals, etc. and may allow us to access the feasible lower limit of barrier thickness in MTJs.

  10. Mercury Oxidation via Catalytic Barrier Filters Phase II

    SciTech Connect

    Wayne Seames; Michael Mann; Darrin Muggli; Jason Hrdlicka; Carol Horabik

    2007-09-30

    In 2004, the Department of Energy National Energy Technology Laboratory awarded the University of North Dakota a Phase II University Coal Research grant to explore the feasibility of using barrier filters coated with a catalyst to oxidize elemental mercury in coal combustion flue gas streams. Oxidized mercury is substantially easier to remove than elemental mercury. If successful, this technique has the potential to substantially reduce mercury control costs for those installations that already utilize baghouse barrier filters for particulate removal. Completed in 2004, Phase I of this project successfully met its objectives of screening and assessing the possible feasibility of using catalyst coated barrier filters for the oxidation of vapor phase elemental mercury in coal combustion generated flue gas streams. Completed in September 2007, Phase II of this project successfully met its three objectives. First, an effective coating method for a catalytic barrier filter was found. Second, the effects of a simulated flue gas on the catalysts in a bench-scale reactor were determined. Finally, the performance of the best catalyst was assessed using real flue gas generated by a 19 kW research combustor firing each of three separate coal types.

  11. Silicon oxide permeation barrier coating of PET bottles and foils

    NASA Astrophysics Data System (ADS)

    Steves, Simon; Deilmann, Michael; Awakowicz, Peter

    2009-10-01

    Modern packaging materials such as polyethylene terephthalate (PET) have displaced established materials in many areas of food and beverage packaging. Plastic packing materials offer are various advantages concerning production and handling. PET bottles for instance are non-breakable and lightweight compared to glass and metal containers. However, PET offers poor barrier properties against gas permeation. Therefore, the shelf live of packaged food is reduced. Permeation of gases can be reduced by depositing transparent plasma polymerized silicon oxide (SiOx) barrier coatings. A microwave (2.45 GHz) driven low pressure plasma reactor is developed based on a modified Plasmaline antenna to treat PET foils or bottles. To increase the barrier properties of the coatings furthermore a RF substrate bias (13.56 MHz) is applied. The composition of the coatings is analyzed by means of Fourier transform infrared (FTIR) spectroscopy regarding carbon and hydrogen content. Influence of gas phase composition and substrate bias on chemical composition of the coatings is discussed. A strong relation between barrier properties and film composition is found: good oxygen barriers are observed as carbon content is reduced and films become quartz-like. Regarding oxygen permeation a barrier improvement factor (BIF) of 70 is achieved.

  12. Evaluation of Oxidation Damage in Thermal Barrier Coating Systems

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Miller, Robert A.

    1996-01-01

    A method based on the technique of dilatometry has been established to quantitatively evaluate the interfacial damage due to the oxidation in a thermal barrier coating system. Strain isolation and adhesion coefficients have been proposed to characterize the thermal barrier coating (TBC) performance based on its thermal expansion behavior. It has been found that, for a thermal barrier coating system consisting of ZrO2-8%Y2O3/FeCrAlY/4140 steel substrate, the oxidation of the bond coat and substrate significantly reduced the ceramic coating adherence, as inferred from the dilatometry measurements. The in-situ thermal expansion measurements under 30 deg C to 700 deg C thermal cycling in air showed that the adhesion coefficient, A(sub i) decreased by 25% during the first 35 oxidation cycles. Metallography showed that delamination occurred at both the ceramic/bond coat and bond coat/substrate interfaces. In addition, the strain isolation effect has been improved by increasing the FeCrAlY bond coat thickness. The strain isolation coefficient, Si, increased from about 0.04 to 0.25, as the bond coat thickness changed from 0.1 mm to 1.0 mm. It may be possible to design optimum values of strain isolation and interface adhesion coefficients to achieve the best TBC performance.

  13. In situ determination of the pore opening point during wet-chemical etching of the barrier layer of porous anodic aluminum oxide: nonuniform impurity distribution in anodic oxide.

    PubMed

    Han, Hee; Park, Sang-Joon; Jang, Jong Shik; Ryu, Hyun; Kim, Kyung Joong; Baik, Sunggi; Lee, Woo

    2013-04-24

    Wet-chemical etching of the barrier oxide layer of anodic aluminum oxide (AAO) was systematically investigated by using scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and a newly devised experimental setup that allows accurate in situ determination of the pore opening point during chemical etching of the barrier oxide layer. We found that opening of the barrier oxide layer by wet-chemical etching can be significantly influenced by anodization time (tanodi). According to secondary ion mass spectrometry (SIMS) analysis, porous anodic aluminum oxide (AAO) samples formed by long-term anodization contained a lower level of anionic impurity in the barrier oxide layer compared to the short-term anodized one and consequently exhibited retarded opening of the barrier oxide layer during the wet-chemical etching. The observed compositional dependence on the anodization time (tanodi) in the barrier oxide layer is attributed to the progressive decrease of the electrolyte concentration upon anodization. The etching rate of the outer pore wall at the bottom part is lower than that of the one at the top part due to the lower level of impurity content in that region. This indicates that a concentration gradient of anionic impurity in the outer pore wall oxide may be established along both the vertical and radial directions of cylindrical pores. Apart from the effect of electrolyte concentration on the chemical composition of the barrier oxide layer, significantly decreased current density arising from the lowered concentration of electrolyte during the long-term anodization (~120 h) was found to cause disordering of pores. The results of the present work are expected to provide viable information not only for practical applications of nanoporous AAO in nanotechnology but also for thorough understanding of the self-organized formation of oxide nanopores during anodization.

  14. Modeling Oxidation Induced Stresses in Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Ferguson, B. L.; Freborg, A. M.; Petrus, G. J.; Brindley, William J.

    1998-01-01

    The use of thermal barrier coatings (TBC's) in gas turbines has increased dramatically in recent years, due mainly to the need for component protection from ever increasing service temperatures. Oxidation of the bond coat has been identified as an important contributing factor to spallation of the ceramic top coat during service. Additional variables found to influence TBC thermal cycle life include bond coat coefficient of thermal expansion, creep behavior of both the ceramic and bond coat layers, and modulus of elasticity. The purpose of this work was to characterize the effects of oxidation on the stress states within the TBC system, as well as to examine the interaction of oxidation with other factors affecting TBC life.

  15. Electrical properties of graphene tunnel junctions with high-κ metal-oxide barriers

    NASA Astrophysics Data System (ADS)

    Feng, Ying; Trainer, Daniel J.; Chen, Ke

    2017-04-01

    An insulating barrier is one of the key components in electronic devices that makes use of quantum tunneling principles. Many metal-oxides have been used as a good barrier material in a tunnel junction for their large band gap, stable chemical properties and superb properties for forming a thin and pin-hole-free insulating layer. The reduced dimensions of transistors have led to the need for alternative, high dielectric constant (high-κ) oxides to replace conventional silicon-based dielectrics to reduce the leaking current induced by electron tunneling. On the other hand, a tunnel junction with one or both electrodes made of graphene may lead to novel applications due to the massless Dirac fermions from the graphene. Here we have fabricated sandwich-type graphene tunnel junctions with high-κ metal-oxides as barriers, including Al2O3, HfO2, ZrO2, and TiO2. Tunneling properties are investigated by observing the temperature and time dependences of the tunneling spectra. Our results show the potential for applications of high-κ oxides in graphene tunnel junctions and bringing new opportunities for memory and logic electronic devices.

  16. All magnesium diboride Josephson junctions with MgO and native oxide barriers

    NASA Astrophysics Data System (ADS)

    Costache, M. V.; Moodera, J. S.

    2010-02-01

    We present results on all-MgB2 tunnel junctions, where the tunnel barrier is deposited MgO or native-oxide of base electrode. For the junctions with MgO, the hysteretic I-V curve resembles a conventional underdamped Josephson junction characteristic with critical current-resistance product nearly independent of the junction area. The dependence of the critical current with temperature up to 20 K agrees with the [Ambegaokar and Baratoff, Phys. Rev. Lett. 10, 486 (1963)] expression. For the junctions with native-oxide, conductance at low bias exhibits subgap features while at high bias reveals thick barriers. As a result no supercurrent was observed in the latter, despite the presence of superconducting-gaps to over 30 K.

  17. Graphene Oxide Bionanocomposite Coatings with High Oxygen Barrier Properties

    PubMed Central

    Uysal Unalan, Ilke; Boyacı, Derya; Ghaani, Masoud; Trabattoni, Silvia; Farris, Stefano

    2016-01-01

    In this work, we present the development of bionanocomposite coatings on poly(ethylene terephthalate) (PET) with outstanding oxygen barrier properties. Pullulan and graphene oxide (GO) were used as main polymer phase and nanobuilding block (NBB), respectively. The oxygen barrier performance was investigated at different filler volume fractions (ϕ) and as a function of different relative humidity (RH) values. Noticeably, the impermeable nature of GO was reflected under dry conditions, in which an oxygen transmission rate (OTR, mL·m−2·24 h−1) value below the detection limit of the instrument (0.01 mL·m−2·24 h−1) was recorded, even for ϕ as low as 0.0004. A dramatic increase of the OTR values occurred in humid conditions, such that the barrier performance was totally lost at 90% RH (the OTR of coated PET films was equal to the OTR of bare PET films). Modelling of the experimental OTR data by Cussler’s model suggested that the spatial ordering of GO sheets within the main pullulan phase was perturbed because of RH fluctuations. In spite of the presence of the filler, all the formulations allowed the obtainment of final materials with haze values below 3%, the only exception being the formulation with the highest loading of GO (ϕ ≈ 0.03). The mechanisms underlying the experimental observations are discussed. PMID:28335372

  18. Correlation between Barrier Width, Barrier Height, and DC Bias Voltage Dependences on the Magnetoresistance Ratio in Ir-Mn Exchange Biased Single and Double Tunnel Junctions

    NASA Astrophysics Data System (ADS)

    Saito, Yoshiaki; Amano, Minoru; Nakajima, Kentaro; Takahashi, Shigeki; Sagoi, Masayuki; Inomata, Koichiro

    2000-10-01

    Dual spin-valve-type double tunnel junctions (DTJs) of Ir-Mn/CoFe/AlOx/Co90Fe10/AlOx/CoFe/Ir-Mn and spin-valve-type single tunnel junctions (STJs) of Ir-Mn/CoFe/AlOx/CoFe/Ni-Fe were fabricated using an ultrahigh vacuum sputtering system, conventional photolithography and ion-beam milling. The STJs could be fabricated with various barrier heights by changing the oxidization conditions during deposition and changing the annealing temperature after deposition, while the AlOx layer thickness remained unchanged. There was a correlation between barrier width, height estimated using Simmons’ expressions, and dc bias voltage dependence on the MR ratio. The VB dependence on the tunneling magnetoresistance (TMR) ratio was mainly related to the barrier width, and the decrease in the TMR ratio with increasing bias voltage is well explained, taking into account the spin-independent two-step tunneling via defect states in the barrier, as a main mechanism, at room temperature. Under optimized oxidization and annealing conditions, the maximum TMR ratio at a low bias voltage, and the dc bias voltage value at which the TMR ratio decreases in value by half (V1/2) were 42.4% and 952 mV in DTJs, and 49.0% and 425 mV in STJs, respectively.

  19. Methane oxidation in a landfill cover with capillary barrier.

    PubMed

    Berger, J; Fornés, L V; Ott, C; Jager, J; Wawra, B; Zanke, U

    2005-01-01

    The methane oxidation potential of a landfill cover with capillary barrier was investigated in an experimental plant (4.8 m x 0.8 m x 2.1m). The cover soil consisted of two layers, a mixture of compost plus sand (0.3 m) over a layer of loamy sand (0.9 m). Four different climatic conditions (summer, winter, spring and fall) were simulated. In and outgoing fluxes were measured. Gas composition, temperature, humidity, matrix potential and gas pressure were monitored in two profiles. CH4 oxidation rate within the investigated top cover ranged from 98% to 57%. The minimum was observed for a short time after irrigation. Temperature distribution, gas concentration profiles and lab-scaled batch experiments indicate that before irrigation the highest oxidising activity took place in a depth of about 30 cm. After irrigation the oxidising horizon seemed to migrate upwards since methanotrophic bacteria develop better there due to an adequate supply with oxygen. It can be assumed that the absence of oxygen is one of the most important limiting factors for the CH4 oxidation process. Abrupt cross-overs between horizons of different soil material may lead to zones of increased water saturation and decreased soil respiration.

  20. MgB2 tunnel junctions with native or thermal oxide barriers

    NASA Astrophysics Data System (ADS)

    Singh, R. K.; Gandikota, R.; Kim, J.; Newman, N.; Rowell, J. M.

    2006-07-01

    MgB2 tunnel junctions (MgB2/barrier/MgB2) were fabricated using a native oxide grown on the bottom MgB2 film as the tunnel barrier. Such barriers therefore survive the deposition of the second electrode at 300°C, even over junction areas of ˜1mm2. Studies of such junctions and those of the type MgB2/native or thermal oxide/metal (Pb, Au, or Ag) show that tunnel barriers grown on MgB2 exhibit a wide range of barrier heights and widths.

  1. MERCURY OXIDIZATION IN NON-THERMAL PLASMA BARRIER DISCHARGE SYSTEM

    SciTech Connect

    V.K. Mathur

    2003-02-01

    In the past decade, the emission of toxic elements from human activities has become a matter of great public concern. Hg, As, Se and Cd typically volatilize during a combustion process and are not easily caught with conventional air pollution control techniques. In addition, there is no pollution prevention technique available now or likely be available in the foreseeable future that can prevent the emission of these trace elements. These trace elements pose additional scientific challenge as they are present at only ppb levels in large gas streams. Mercury, in particular, has attracted significant attention due to its high volatility, toxicity and potential threat to human health. In the present research work, a non-thermal plasma dielectric barrier discharge technique has been used to oxidize Hg{sup 0}(g) to HgO. The basic premise of this approach is that Hg{sup 0} in vapor form cannot be easily removed in an absorption tower whereas HgO as a particulate is amiable to water scrubbing. The work presented in this report consists of three steps: (1) setting-up of an experimental apparatus to generate mercury vapors at a constant rate and modifying the existing non-thermal plasma reactor system, (2) solving the analytical challenge for measuring mercury vapor concentration at ppb level, and (3) conducting experiments on mercury oxidation under plasma conditions to establish proof of concept.

  2. Investigation of special features of parameters of Schottky barrier contacts caused by a nonlinear bias dependence of the barrier height

    NASA Astrophysics Data System (ADS)

    Bozhkov, V. G.; Shmargunov, A. V.

    2012-03-01

    The results of studying the IV-characteristics (IVCs) of the contact Au-n-GaAs obtained by electrochemical deposition are presented. The observed characteristics - the bias dependence of the ideality factor (n), the measured (ϕbm) and effective (ϕbI) barrier heights, an inverse relationship between the measured barrier height and ideality factor, and the edge effects (the dependence of n, ϕbm, and ϕbI on the contact diameter) are explained by the nonlinear bias dependence on the effective barrier height. The explanation is given on the basis of the contact model with an intermediate layer and interface states (Bardeen model), and the intimate contact model with the subsurface states. The nonlinearity of the bias dependence on the barrier height is due to the inhomogeneous energy distribution of the interface states (a decrease in density from the edges to the middle of the bandgap) and the inhomogeneous energy and coordinate (from the surface to the depth) distribution of the subsurface states. An essential feature for every model is also the condition that the barrier height and ideality factor are measured at a constant current (or in a constant range of currents) while studying contacts with different diameters or when measuring the IVCs at different temperatures. This condition is not difficult to achieve, but gives the necessary certainty to different barrier height values used in examining experimental results. Some limitations and shortcomings of the widely used model of inhomogeneous Schottky barrier contact with the "saddle points" are also discussed.

  3. Criegee intermediate reaction with CO: mechanism, barriers, conformer-dependence, and implications for ozonolysis chemistry.

    PubMed

    Kumar, Manoj; Busch, Daryle H; Subramaniam, Bala; Thompson, Ward H

    2014-03-13

    Density functional theory and transition state theory rate constant calculations have been performed to gain insight into the bimolecular reaction of the Criegee intermediate (CI) with carbon monoxide (CO) that is proposed to be important in both atmospheric and industrial chemistry. A new mechanism is suggested in which the CI acts as an oxidant by transferring an oxygen atom to the CO, resulting in the formation of a carbonyl compound (aldehyde or ketone depending upon the CI) and carbon dioxide. Fourteen different CIs, including ones resulting from biogenic ozonolysis, are considered. Consistent with previous reports for other CI bimolecular reactions, the anti conformers are found to react faster than the syn conformers. However, this can be attributed to steric effects and not hyperconjugation as generally invoked. The oxidation reaction is slow, with barrier heights between 6.3 and 14.7 kcal/mol and estimated reaction rate constants 6-12 orders-of-magnitude smaller than previously reported literature estimates. The reaction is thus expected to be unimportant in the context of tropospheric oxidation chemistry. However, the reaction mechanism suggests that CO could be exploited in ozonolysis to selectively obtain industrially important carbonyl compounds.

  4. Intracellular mediators of JAM-A-dependent epithelial barrier function.

    PubMed

    Monteiro, Ana C; Parkos, Charles A

    2012-06-01

    Junctional adhesion molecule-A (JAM-A) is a critical signaling component of the apical junctional complex, a structure composed of several transmembrane and scaffold molecules that controls the passage of nutrients and solutes across epithelial surfaces. Observations from JAM-A-deficient epithelial cells and JAM-A knockout animals indicate that JAM-A is an important regulator of epithelial paracellular permeability; however, the mechanism(s) linking JAM-A to barrier function are not understood. This review highlights recent findings relevant to JAM-A-mediated regulation of epithelial permeability, focusing on the role of upstream and downstream signaling candidates. We draw on what is known about proteins reported to associate with JAM-A in other pathways and on known modulators of barrier function to propose candidate effectors that may mediate JAM-A regulation of epithelial paracellular permeability. Further investigation of pathways highlighted in this review may provide ideas for novel therapeutics that target debilitating conditions associated with barrier dysfunction, such as inflammatory bowel disease.

  5. Comparison between two models of absorption of matter waves by a thin time-dependent barrier

    NASA Astrophysics Data System (ADS)

    Barbier, Maximilien; Beau, Mathieu; Goussev, Arseni

    2015-11-01

    We report a quantitative, analytical, and numerical comparison between two models of the interaction of a nonrelativistic quantum particle with a thin time-dependent absorbing barrier. The first model represents the barrier by a set of time-dependent discontinuous matching conditions, which are closely related to Kottler boundary conditions used in stationary-wave optics as a mathematical basis for Kirchhoff diffraction theory. The second model mimics the absorbing barrier with an off-diagonal δ potential with a time-dependent amplitude. We show that the two models of absorption agree in their predictions in a semiclassical regime, the regime readily accessible in modern experiments with ultracold atoms.

  6. Non-thermal dielectric-barrier discharge plasma damages human keratinocytes by inducing oxidative stress.

    PubMed

    Kim, Ki Cheon; Piao, Mei Jing; Madduma Hewage, Susara Ruwan Kumara; Han, Xia; Kang, Kyoung Ah; Jo, Jin Oh; Mok, Young Sun; Shin, Jennifer H; Park, Yeunsoo; Yoo, Suk Jae; Hyun, Jin Won

    2016-01-01

    The aim of this study was to identify the mechanisms through which dielectric-barrier discharge plasma damages human keratinocytes (HaCaT cells) through the induction of oxidative stress. For this purpose, the cells were exposed to surface dielectric-barrier discharge plasma in 70% oxygen and 30% argon. We noted that cell viability was decreased following exposure of the cells to plasma in a time-dependent manner, as shown by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. The levels of intracellular reactive oxygen species (ROS) were determined using 2',7'-dichlorodihydrofluorescein diacetate and dihydroethidium was used to monitor superoxide anion production. Plasma induced the generation of ROS, including superoxide anions, hydrogen peroxide and hydroxyl radicals. N-acetyl cysteine, which is an antioxidant, prevented the decrease in cell viability caused by exposure to plasma. ROS generated by exposure to plasma resulted in damage to various cellular components, including lipid membrane peroxidation, DNA breaks and protein carbonylation, which was detected by measuring the levels of 8-isoprostane and diphenyl-1-pyrenylphosphine assay, comet assay and protein carbonyl formation. These results suggest that plasma exerts cytotoxic effects by causing oxidative stress-induced damage to cellular components.

  7. Non-thermal dielectric-barrier discharge plasma damages human keratinocytes by inducing oxidative stress

    PubMed Central

    KIM, KI CHEON; PIAO, MEI JING; HEWAGE, SUSARA RUWAN KUMARA MADDUMA; HAN, XIA; KANG, KYOUNG AH; JO, JIN OH; MOK, YOUNG SUN; SHIN, JENNIFER H.; PARK, YEUNSOO; YOO, SUK JAE; HYUN, JIN WON

    2016-01-01

    The aim of this study was to identify the mechanisms through which dielectric-barrier discharge plasma damages human keratinocytes (HaCaT cells) through the induction of oxidative stress. For this purpose, the cells were exposed to surface dielectric-barrier discharge plasma in 70% oxygen and 30% argon. We noted that cell viability was decreased following exposure of the cells to plasma in a time-dependent manner, as shown by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. The levels of intracellular reactive oxygen species (ROS) were determined using 2′,7′-dichlorodihydro-fluorescein diacetate and dihydroethidium was used to monitor superoxide anion production. Plasma induced the generation of ROS, including superoxide anions, hydrogen peroxide and hydroxyl radicals. N-acetyl cysteine, which is an antioxidant, prevented the decrease in cell viability caused by exposure to plasma. ROS generated by exposure to plasma resulted in damage to various cellular components, including lipid membrane peroxidation, DNA breaks and protein carbonylation, which was detected by measuring the levels of 8-isoprostane and diphenyl-1-pyrenylphosphine assay, comet assay and protein carbonyl formation. These results suggest that plasma exerts cytotoxic effects by causing oxidative stress-induced damage to cellular components. PMID:26573561

  8. Temperature dependent barrier height and ideality factor of electrodeposited n-CdSe/Cu Schottky barrier diode

    NASA Astrophysics Data System (ADS)

    Mahato, S.; Shiwakoti, N.; Kar, A. K.

    2015-06-01

    This article reports the measurement of temperature-dependent barrier height and ideality factor of n-CdSe/Cu Schottky barrier diode. The Cadmium Selenide (CdSe) thin films have been deposited by simple electrodeposition technique. The XRD measurements ravels the deposited single phase CdSe films are highly oriented on (002) plane and the average particle size has been calculated to be ~18 nm. From SEM characterization, it is clear that the surface of CdSe thin films are continuous, homogeneous and the film is well adhered to the substrate and consists of fine grains which are irregular in shape and size. Current-Voltage characteristics have been measured at different temperatures in the range (298 K - 353 K). The barrier height and ideality factor are found to be strongly temperature dependent. The inhomogenious barrier height increases and ideality factor decreases with increase in temperature. The expectation value has been calculated and its value is 0.30 eV.

  9. Temperature dependent barrier height and ideality factor of electrodeposited n-CdSe/Cu Schottky barrier diode

    SciTech Connect

    Mahato, S. Shiwakoti, N.; Kar, A. K.

    2015-06-24

    This article reports the measurement of temperature-dependent barrier height and ideality factor of n-CdSe/Cu Schottky barrier diode. The Cadmium Selenide (CdSe) thin films have been deposited by simple electrodeposition technique. The XRD measurements ravels the deposited single phase CdSe films are highly oriented on (002) plane and the average particle size has been calculated to be ~18 nm. From SEM characterization, it is clear that the surface of CdSe thin films are continuous, homogeneous and the film is well adhered to the substrate and consists of fine grains which are irregular in shape and size. Current-Voltage characteristics have been measured at different temperatures in the range (298 K – 353 K). The barrier height and ideality factor are found to be strongly temperature dependent. The inhomogenious barrier height increases and ideality factor decreases with increase in temperature. The expectation value has been calculated and its value is 0.30 eV.

  10. Dependence of Andreev reflection and Schottky barriers on GaMnAs/Nb interface treatment

    SciTech Connect

    Eid, K. F. Dahliah, D. F.; Abujeib, H. A.; Liu, X.; Furdyna, J. K.

    2015-05-07

    We studied the interfacial contact between GaMnAs and superconducting Nb micro-structures both with and without removing the native GaMnAs surface oxide. Our results show that a strong Schottky barrier forms at the interface when the oxide layer is left between Nb and GaMnAs. This barrier can be confused for Andreev Reflection and erroneously used to extract spin polarization. A simple acid etch is shown to remove the oxide film, thus decreasing the interface resistance, removing the Schottky barrier, and causing a clear Andreev reflection effect. One key recommendation for point contact Andreev reflection studies is to push the tip hard enough into contact and verify that the total resistance is not too high.

  11. Influence of the nonlinear bias dependence of the barrier height on measured Schottky-barrier contact parameters

    NASA Astrophysics Data System (ADS)

    Bozhkov, V. G.; Shmargunov, A. V.

    2011-06-01

    A numerical investigation of current-voltage characteristics (IVCs) of the ideal metal-semiconductor Schottky-barrier contact (SBC) metal-n-GaAs in the wide range of temperatures, contact diameters and doping levels considering the influence of image force and tunneling effects is presented. The analysis is carried out on the basis of model, taking into account the nonlinear bias dependence of the barrier height (generally, effective one) and assuming that the SBC parameters are determined at constant (specified) current value in the temperature or contact diameter ranges, which corresponds practically to experimental conditions of measurement of SBC parameters. It is shown that such SBCs have behavior peculiarities typical for most real contacts: the "low temperature anomaly" (the ideality factor n increase and the barrier height ϕbm (measured by the saturation current) decrease with temperature decrease), edge effects (increase of n and decrease of ϕbm with contact diameter decrease), the inverse connection between ϕbm and n, when the growth of one of them is followed by the decrease of the other. A simple and very precise analytic representation of the IVC is given for the SBC in wide temperature and doping level ranges. This representation agrees closely with known experimental results. The high-accuracy method of the barrier height determining is proposed on this basis.

  12. Barriers to Quitting Smoking Among Substance Dependent Patients Predict Smoking Cessation Treatment Outcome.

    PubMed

    Martin, Rosemarie A; Cassidy, Rachel N; Murphy, Cara M; Rohsenow, Damaris J

    2016-05-01

    For smokers with substance use disorders (SUD), perceived barriers to quitting smoking include concerns unique to effects on sobriety as well as usual concerns. We expanded our Barriers to Quitting Smoking in Substance Abuse Treatment (BQS-SAT) scale, added importance ratings, validated it, and then used the importance scores to predict smoking treatment response in smokers with substance use disorders (SUD) undergoing smoking treatment in residential treatment programs in two studies (n=184 and 340). Both components (general barriers, weight concerns) were replicated with excellent internal consistency reliability. Construct validity was supported by significant correlations with pretreatment nicotine dependence, smoking variables, smoking self-efficacy, and expected effects of smoking. General barriers significantly predicted 1-month smoking abstinence, frequency and heaviness, and 3-month smoking frequency; weight concerns predicted 1-month smoking frequency. Implications involve addressing barriers with corrective information in smoking treatment for smokers with SUD.

  13. Methamphetamine disrupts blood-brain barrier function by induction of oxidative stress in brain endothelial cells.

    PubMed

    Ramirez, Servio H; Potula, Raghava; Fan, Shongshan; Eidem, Tess; Papugani, Anil; Reichenbach, Nancy; Dykstra, Holly; Weksler, Babette B; Romero, Ignacio A; Couraud, Pierre O; Persidsky, Yuri

    2009-12-01

    Methamphetamine (METH), a potent stimulant with strong euphoric properties, has a high abuse liability and long-lasting neurotoxic effects. Recent studies in animal models have indicated that METH can induce impairment of the blood-brain barrier (BBB), thus suggesting that some of the neurotoxic effects resulting from METH abuse could be the outcome of barrier disruption. In this study, we provide evidence that METH alters BBB function through direct effects on endothelial cells and explore possible underlying mechanisms leading to endothelial injury. We report that METH increases BBB permeability in vivo, and exposure of primary human brain microvascular endothelial cells (BMVEC) to METH diminishes the tightness of BMVEC monolayers in a dose- and time-dependent manner by decreasing the expression of cell membrane-associated tight junction (TJ) proteins. These changes were accompanied by the enhanced production of reactive oxygen species, increased monocyte migration across METH-treated endothelial monolayers, and activation of myosin light chain kinase (MLCK) in BMVEC. Antioxidant treatment attenuated or completely reversed all tested aspects of METH-induced BBB dysfunction. Our data suggest that BBB injury is caused by METH-mediated oxidative stress, which activates MLCK and negatively affects the TJ complex. These observations provide a basis for antioxidant protection against brain endothelial injury caused by METH exposure.

  14. Phase stability of thermal barrier oxides based on t'-zirconia with trivalent oxide additions

    NASA Astrophysics Data System (ADS)

    Rebollo Franco, Noemi Rosa

    Zirconia stabilized with 7+/-1 wt.% addition of yttria (7YSZ) is widely used for thermal barrier coatings (TBC's) on actively cooled gas turbine components, selected partly because of its superior durability under thermal cyclic conditions. As deposited, 7YSZ occurs as a metastable single-phase tetragonal solid solution (t') that is thermodynamically stable against the deleterious transformation to monoclinic upon cooling. However, at high temperatures t' is driven to decompose diffusionally into an equilibrium mixture of high-Y cubic and low-Y tetragonal; the latter becomes transformable to monoclinic compromising the mechanical integrity of the system. This dissertation explores the effects of trivalent stabilizers, including Y, Sc and selected rare-earth oxides (REO's), on the phase stability of the resulting solid solutions in zirconia. The REO additions are of interest because they can potentially enhance the insulation efficiency on the coating allowing higher operating temperatures. However, understanding of their effects on phase stability and potentially on cyclic durability at the projected use temperature in next generation engines (1200-1400°C) is insufficient to guide the design of coatings with the desirable combination of lower thermal conductivity and acceptable durability. Sc was also investigated because of previous reports on the higher phase stability of materials doped with Sc, and Y served as the baseline. The experimental approach is based on powders synthesized by reverse co-precipitation of precursor solutions, usually compacted and then subjected to a variety of heat treatments, following their evolution by means of X-ray diffractometry, dilatometry, transmission electron microscopy and Raman spectroscopy. The use of powders facilitated the synthesis of a wider range of compositions that would not have been possible by coating deposition approaches, and because the synthesis occurs at low temperature, it also enabled the starting

  15. Spin-dependent tunneling junctions with AlN and AlON barriers

    NASA Astrophysics Data System (ADS)

    Sharma, Manish; Nickel, Janice H.; Anthony, Thomas C.; Wang, Shan X.

    2000-10-01

    We report on ferromagnetic spin-dependent tunneling (SDT) junctions with NiFe/AlN/NiFe and NiFe/AlON/NiFe structures. Good barriers were formed by plasma nitridation and oxy-nitridation of Al films. Tunneling magnetoresistance ratios (TMR) up to 18% were observed at room temperature. The devices exhibit lower resistance-area products than those seen in reference junctions with Al2O3 barriers. The degradation in TMR at higher bias voltages is found to be less than that found in standard alumina junctions. AlN and AlON could thus be alternate materials for the tunnel barrier in SDT junctions.

  16. Advanced Multi-Component Defect Cluster Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Miller, Robert A.

    1990-01-01

    The advantages of using ceramic thermal barrier coatings in gas turbine engine hot sections include increased fuel efficiency and improved engine reliability. However, current thermal barrier coatings will not have the low thermal conductivity and necessary sintering resistance under higher operating temperatures and thermal gradients required by future advanced ultra-efficient and low-emission aircraft engines. In this paper, a novel oxide defect cluster design approach is described for achieving low thermal conductivity and excellent thermal stability of the thermal barrier coating systems. This approach utilizes multi-component rare earth and other metal cluster oxide dopants that are incorporated in the zirconia-yttria based systems, thus significantly reducing coating thermal conductivity and sintering resistance by effectively promoting the formation of thermodynamically stable, essentially immobile defect clusters and/or nanoscale phases. The performance of selected plasma-sprayed cluster oxide thermal barrier coating systems has been evaluated. The advanced multi-component thermal barrier coating systems were found to have significantly lower initial and long-term thermal conductivities, and better high temperature stability. The effect of oxide cluster dopants on coating thermal conductivity, sintering resistance, oxide grain growth behavior and durability will be discussed.

  17. Advanced Multi-Component Defect Cluster Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Miller, Robert A.

    2003-01-01

    The advantages of using ceramic thermal barrier coatings in gas turbine engine hot sections include increased fuel efficiency and improved engine reliability. However, current thermal barrier coatings will not have the low thermal conductivity and necessary sintering resistance under higher operating temperatures and thermal gradients required by future advanced ultra efficient and low emission aircraft engines. In this paper, a novel oxide defect cluster design approach is described for achieving low thermal conductivity and excellent thermal stability of the thermal barrier coating systems. This approach utilizes multi-component rare earth and other metal cluster oxide dopants that are incorporated in the zirconia-yttna based systems, thus significantly reducing coating thermal conductivity and sintering resistance by effectively promoting the formation of thermodynamically stable, essentially immobile defect clusters and/or nanoscale phases. The performance of selected plasma-sprayed cluster oxide thermal barrier coating systems has been evaluated. The advanced multi-component thermal barrier coating systems were found to have significantly lower initial and long-term thermal conductivities, and better high temperature stability. The effect of oxide cluster dopants on coating thermal conductivity, sintering resistance, oxide grain growth behavior and durability will be discussed.

  18. Coherent magnetotunneling based on (001) magnesium oxide barrier

    NASA Astrophysics Data System (ADS)

    Mazumdar, Dipanjan

    2007-12-01

    Spintronics (spin-based electronics) is an emerging field which relies on the electronic spin degree of freedom to create superior devices. In 2001, first-principles calculations predicted extremely large magnetoresistance (MR) of well over 1000% in magnetic tunnel junctions (MTJs) that used (001) MgO as the insulating barrier. This large effect is achieved when conduction electrons conserve their symmetry inside the barrier, leading to spin-coherent tunneling. Since then, a few experimental groups, which include our group at Brown, have successfully realized high MR values on such systems. I shall present our recent work on MTJs with (001) MgO tunnel barrier. After a brief introduction of the MR effect, I shall focus on the fabrication and room temperature transport properties of MgO-based MTJs with MR values of over 200%. Also, these MTJs are highly suitable for low magnetic field sensing. In the later half, I shall describe our investigations of the low frequency noise in these devices. Noise spectra are 1/f, and scales with the field sensitivity of the MTJ, indicating that the noise arises predominantly from intrinsic magnetization fluctuations. Special attention was paid to reduce the magnetic field noise level. We show that the application of an external hard-axis bias field significantly reduces this noise by suppressing the magnetic fluctuations.

  19. Healthcare Preferences among Nursing Home Residents: Perceived Barriers and Situational Dependencies

    PubMed Central

    Bangerter, Lauren R.; Abbott, Katherine; Heid, Allison R.; Klumpp, Rachel E.; Van Haitsma, Kimberly

    2016-01-01

    While much research has examined end of life care preferences of nursing home (NH) residents, little work has examined resident preferences for everyday healthcare. The present study conducted interviews with 255 residents recruited from 35 NHs. Content analysis identified barriers (hindrances to the fulfillment of resident preferences) and situational dependencies (what would make residents change their mind about the importance of these preferences) associated with preferences for utilizing mental health services, choosing a medical care provider, and choosing individuals involved in care discussions. Barriers and situational dependencies were embedded within the person, facility environment, and social environment. Nearly half of residents identified barriers to their preferences of choosing others involved in care and choosing a medical care provider. In contrast, the importance of mental health services was situationally dependent on needs of residents. Results highlight opportunities for improvement in practice and facility policies that promote person-centered care. PMID:26716460

  20. Amorphous alumina thin films deposited on titanium: Interfacial chemistry and thermal oxidation barrier properties

    SciTech Connect

    Baggetto, Loic; Charvillat, Cedric; Thebault, Yannick; Esvan, Jerome; Lafont, Marie-Christine; Scheid, Emmanuel; Veith, Gabriel M.; Vahlas, Constantin

    2015-12-02

    Ti/Al2O3 bilayer stacks are used as model systems to investigate the role of atomic layer deposition (ALD) and chemical vapor deposition (CVD) to prepare 30-180 nm thick amorphous alumina films as protective barriers for the medium temperature oxidation (500-600⁰C) of titanium, which is employed in aeronautic applications. X-ray diffraction (XRD), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS) results show that the films produced from the direct liquid injection (DLI) CVD of aluminum tri-isopropoxide (ATI) are poor oxygen barriers. The films processed using the ALD of trimethylaluminum (TMA) show good barrier properties but an extensive intermixing with Ti which subsequently oxidizes. In contrast, the films prepared from dimethyl aluminum isopropoxide (DMAI) by CVD are excellent oxygen barriers and show little intermixing with Ti. Overall, these measurements correlate the effect of the alumina coating thickness, morphology, and stoichiometry resulting from the preparation method to the oxidation barrier properties, and show that compact and stoichiometric amorphous alumina films offer superior barrier properties.

  1. Amorphous alumina thin films deposited on titanium: Interfacial chemistry and thermal oxidation barrier properties

    DOE PAGES

    Baggetto, Loic; Charvillat, Cedric; Thebault, Yannick; ...

    2015-12-02

    Ti/Al2O3 bilayer stacks are used as model systems to investigate the role of atomic layer deposition (ALD) and chemical vapor deposition (CVD) to prepare 30-180 nm thick amorphous alumina films as protective barriers for the medium temperature oxidation (500-600⁰C) of titanium, which is employed in aeronautic applications. X-ray diffraction (XRD), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS) results show that the films produced from the direct liquid injection (DLI) CVD of aluminum tri-isopropoxide (ATI) are poor oxygen barriers. The films processed using the ALD of trimethylaluminum (TMA) show good barrier properties butmore » an extensive intermixing with Ti which subsequently oxidizes. In contrast, the films prepared from dimethyl aluminum isopropoxide (DMAI) by CVD are excellent oxygen barriers and show little intermixing with Ti. Overall, these measurements correlate the effect of the alumina coating thickness, morphology, and stoichiometry resulting from the preparation method to the oxidation barrier properties, and show that compact and stoichiometric amorphous alumina films offer superior barrier properties.« less

  2. Nox2-dependent glutathionylation of endothelial NOS leads to uncoupled superoxide production and endothelial barrier dysfunction in acute lung injury.

    PubMed

    Wu, Feng; Szczepaniak, William S; Shiva, Sruti; Liu, Huanbo; Wang, Yinna; Wang, Ling; Wang, Ying; Kelley, Eric E; Chen, Alex F; Gladwin, Mark T; McVerry, Bryan J

    2014-12-15

    Microvascular barrier integrity is dependent on bioavailable nitric oxide (NO) produced locally by endothelial NO synthase (eNOS). Under conditions of limited substrate or cofactor availability or by enzymatic modification, eNOS may become uncoupled, producing superoxide in lieu of NO. This study was designed to investigate how eNOS-dependent superoxide production contributes to endothelial barrier dysfunction in inflammatory lung injury and its regulation. C57BL/6J mice were challenged with intratracheal LPS. Bronchoalveolar lavage fluid was analyzed for protein accumulation, and lung tissue homogenate was assayed for endothelial NOS content and function. Human lung microvascular endothelial cell (HLMVEC) monolayers were exposed to LPS in vitro, and barrier integrity and superoxide production were measured. Biopterin species were quantified, and coimmunoprecipitation (Co-IP) assays were performed to identify protein interactions with eNOS that putatively drive uncoupling. Mice exposed to LPS demonstrated eNOS-dependent increased alveolar permeability without evidence for altered canonical NO signaling. LPS-induced superoxide production and permeability in HLMVEC were inhibited by the NOS inhibitor nitro-l-arginine methyl ester, eNOS-targeted siRNA, the eNOS cofactor tetrahydrobiopterin, and superoxide dismutase. Co-IP indicated that LPS stimulated the association of eNOS with NADPH oxidase 2 (Nox2), which correlated with augmented eNOS S-glutathionylation both in vitro and in vivo. In vitro, Nox2-specific inhibition prevented LPS-induced eNOS modification and increases in both superoxide production and permeability. These data indicate that eNOS uncoupling contributes to superoxide production and barrier dysfunction in the lung microvasculature after exposure to LPS. Furthermore, the results implicate Nox2-mediated eNOS-S-glutathionylation as a mechanism underlying LPS-induced eNOS uncoupling in the lung microvasculature.

  3. Thin Oxides as a Cu Diffusion Barrier for NIF Be Ablator Capsules

    SciTech Connect

    Youngblood, Kelly P.; Huang, H.; Xu, H. W.; Hayes, J.; Moreno, K. A.; Wu, J. J.; Nikroo, A.; Alford, C. A.; Hamza, A. V.; Kucheyev, S. O.; Wang, Y. M.; Wu, K. J.

    2013-03-01

    The NIF point design uses a five-layer capsule to modify the X-ray absorption in order to achieve optimized shock timing. A stepped copper dopant design defines the layer structure. The production of the capsule involves pyrolysis to remove the inner plastic mandrel. Copper atoms diffuse radially and azimuthally throughout the capsule during pyrolysis. This diffusion significantly diminishes the capsule performance during implosion. Thermal and coated oxide barrier layers employed between layers mitigate the diffusion of copper during the mandrel removal process. The copper atoms do not diffuse through this barrier during pyrolysis. A capsule fabrication method that produces a capsule with a thin oxide layer will be discussed.

  4. Highly defective oxides as sinter resistant thermal barrier coating

    DOEpatents

    Subramanian, Ramesh

    2005-08-16

    A thermal barrier coating material formed of a highly defective cubic matrix structure having a concentration of a stabilizer sufficiently high that the oxygen vacancies created by the stabilizer interact within the matrix to form multi-vacancies, thereby improving the sintering resistance of the material. The concentration of stabilizer within the cubic matrix structure is greater than that concentration of stabilizer necessary to give the matrix a peak ionic conductivity value. The concentration of stabilizer may be at least 30 wt. %. Embodiments include a cubic matrix of zirconia stabilized by at least 30-50 wt. % yttria, and a cubic matrix of hafnia stabilized by at least 30-50 wt. % gadolinia.

  5. Temperature-dependent electrical transport properties of (Au/Ni)/n-GaN Schottky barrier diodes

    NASA Astrophysics Data System (ADS)

    Dogan, Hulya; Elagoz, Sezai

    2014-09-01

    The temperature-dependent electrical properties of (Au/Ni)/n-GaN Schottky barrier diodes (SBDs)have been investigated in the wide temperature range of 40-400 K. The analysis of the main electrical characteristics such as zero-bias barrier height (ΦB0), ideality factor (n) and series resistance (Rs) were found strongly temperature dependent. Such behavior is attributed to barrier inhomogeneities by assuming a Gaussian distribution (GD) of barrier heights (BHs) at the interface. It is evident that the diode parameters such as zero-bias barrier height increases and the ideality factor decreases with increasing temperature. The values of series resistance that are obtained from Cheung's method are decreasing with increasing temperature. The temperature dependence of Schottky barrier height (SBD) and ideality factor (n) are explained by invoking three sets of Gaussian distribution of (SBH) in the temperature ranges of 280-400 K, 120-260 K and 40-100 K, respectively. (Au/Ni)/n-GaN Schottky barrier diode have been shown a Gaussian distribution giving mean BHs (ΦbarB0) of 1.167, 0.652 and 0.356 eV and standard deviation σs of 0.178, 0.087 and 0.133 V for the three temperature regions. A modified ln(I0/T2)-q2σ2/2k2T2 vs. 1/kT plot have given ΦbarB0 and A* as 1.173 eV and 34.750 A/cm2 K2, 0.671 eV and 26.293 A/cm2 K2, 0.354 eV and 10.199 A/cm2 K2, respectively.

  6. Oxidation Resistance: One Barrier to Moving Beyond Ni-Base Superalloys

    SciTech Connect

    Pint, Bruce A; Distefano, James R; Wright, Ian G

    2006-01-01

    The implementation of new high-temperature materials is often hampered by their lack of oxidation or environmental resistance. This failing is one of the strongest barriers to moving beyond Ni-base superalloys for many commercial applications. In practice, usable high-temperature alloys have at least reasonable oxidation resistance, but the current generation of single-crystal Ni-base superalloys has sufficient oxidation resistance that optimized versions can be used without a metallic bond coating and only an oxygen-transparent ceramic coating for thermal protection. The material development process often centers around mechanical properties, while oxidation resistance, along with other realities, is given minor attention. For many applications, the assumption that an oxidation-resistant coating can be used to protect a substrate is seriously flawed, as coatings often do not provide sufficient reliability for critical components. Examples of oxidation problems are given for currently used materials and materials classes with critical oxidation resistance problems.

  7. Radiation dose dependent change in physiochemical, mechanical and barrier properties of guar gum based films.

    PubMed

    Saurabh, Chaturbhuj K; Gupta, Sumit; Bahadur, Jitendra; Mazumder, S; Variyar, Prasad S; Sharma, Arun

    2013-11-06

    Mechanical and water vapor barrier properties of biodegradable films prepared from radiation processed guar gum were investigated. Films prepared from GG irradiated up to 500 Gy demonstrated significantly higher tensile strength as compared to non-irradiated control films. This improvement in tensile strength observed was demonstrated to be due to the ordering of polymer structures as confirmed by small angle X-ray scattering analysis. Exposure to doses higher than 500 Gy, however, resulted in a dose dependent decrease in tensile strength. A dose dependent decrease in puncture strength with no significant differences in the percent elongation was also observed at all the doses studied. Water vapor barrier properties of films improved up to 15% due to radiation processing. Radiation processing at lower doses for improving mechanical and barrier properties of guar based packaging films is demonstrated here for the first time.

  8. Application of diffusion barriers to the refractory fibers of tungsten, columbium, carbon and aluminum oxide

    NASA Technical Reports Server (NTRS)

    Douglas, F. C.; Paradis, E. L.; Veltri, R. D.

    1973-01-01

    A radio frequency powered ion-plating system was used to plate protective layers of refractory oxides and carbide onto high strength fiber substrates. Subsequent overplating of these combinations with nickel and titanium was made to determine the effectiveness of such barrier layers in preventing diffusion of the overcoat metal into the fibers with consequent loss of fiber strength. Four substrates, five coatings, and two metal matrix materials were employed for a total of forty material combinations. The substrates were tungsten, niobium, NASA-Hough carbon, and Tyco sapphire. The diffusion-barrier coatings were aluminum oxide, yttrium oxide, titanium carbide, tungsten carbide with 14% cobalt addition, and zirconium carbide. The metal matrix materials were IN 600 nickel and Ti 6/4 titanium. Adhesion of the coatings to all substrates was good except for the NASA-Hough carbon, where flaking off of the oxide coatings in particular was observed.

  9. Comparison study of ferrofluid and powder iron oxide nanoparticle permeability across the blood-brain barrier.

    PubMed

    Hoff, Dan; Sheikh, Lubna; Bhattacharya, Soumya; Nayar, Suprabha; Webster, Thomas J

    2013-01-01

    In the present study, the permeability of 11 different iron oxide nanoparticle (IONP) samples (eight fluids and three powders) was determined using an in vitro blood-brain barrier model. Importantly, the results showed that the ferrofluid formulations were statistically more permeable than the IONP powder formulations at the blood-brain barrier, suggesting a role for the presently studied in situ synthesized ferrofluid formulations using poly(vinyl) alcohol, bovine serum albumin, collagen, glutamic acid, graphene, and their combinations as materials which can cross the blood-brain barrier to deliver drugs or have other neurological therapeutic efficacy. Conversely, the results showed the least permeability across the blood-brain barrier for the IONP with collagen formulation, suggesting a role as a magnetic resonance imaging contrast agent but limiting IONP passage across the blood-brain barrier. Further analysis of the data yielded several trends of note, with little correlation between permeability and fluid zeta potential, but a larger correlation between permeability and fluid particle size (with the smaller particle sizes having larger permeability). Such results lay the foundation for simple modification of iron oxide nanoparticle formulations to either promote or inhibit passage across the blood-brain barrier, and deserve further investigation for a wide range of applications.

  10. Use of aluminum as an oxidation barrier for titanium

    NASA Technical Reports Server (NTRS)

    Unnam, J.; Shenoy, R. N.; Wiedemann, K. E.; Clark, R. K.

    1985-01-01

    A study is conducted of the use of aluminum coatings as oxidation retardants for Ti alloys, using room temperature normal emittance and spectral emittance as bases for the characterization of oxidation properties with and without the coatings. Thermal exposures were conducted in a thermogravimetric analysis apparatus in which specimen weight was continuously monitored. The results obtained indicate that the weight gains are proportional to the square root of the time for uncoated alloys and for 649 C-exposed aluminum-coated alloys. For the 704 C-exposed aluminum-coated alloys, weight gain exhibits a low rate for short and a high rate for long exposure times, implying that the 0.5-micron coating's protection decreases for long exposures at this temperature.

  11. Asymmetric spin absorption across a low-resistance oxide barrier

    SciTech Connect

    Chen, Shuhan; Qin, Chuan; Ji, Yi

    2015-07-21

    An unconventional method of nonlocal spin detection is demonstrated in mesoscopic lateral spin valves at room temperature. Clear nonlocal spin signals are detected between the two ends of an extended ferromagnetic spin detector. This is different from the conventional method in which the nonlocal voltage is measured between the spin detector and the nonmagnetic channel. The results can be understood as spatially non-uniform absorption of a pure spin current into the spin detector across a low-resistance oxide interface.

  12. Vasoinhibins regulate the inner and outer blood-retinal barrier and limit retinal oxidative stress

    PubMed Central

    Arredondo Zamarripa, David; Díaz-Lezama, Nundehui; Meléndez García, Rodrigo; Chávez Balderas, Jesús; Adán, Norma; Ledesma-Colunga, Maria G.; Arnold, Edith; Clapp, Carmen; Thebault, Stéphanie

    2014-01-01

    Vasoinhibins are prolactin fragments present in the retina, where they have been shown to prevent the hypervasopermeability associated with diabetes. Enhanced bradykinin (BK) production contributes to the increased transport through the blood-retina barrier (BRB) in diabetes. Here, we studied if vasoinhibins regulate BRB permeability by targeting the vascular endothelium and retinal pigment epithelium (RPE) components of this barrier. Intravitreal injection of BK in male rats increased BRB permeability. Vasoinhibins prevented this effect, as did the B2 receptor antagonist Hoe-140. BK induced a transient decrease in mouse retinal and brain capillary endothelial monolayer resistance that was blocked by vasoinhibins. Both vasoinhibins and the nitric oxide (NO) synthase inhibitor L-NAME, but not the antioxidant N-acetyl cysteine (NAC), blocked the transient decrease in bovine umbilical vein endothelial cell (BUVEC) monolayer resistance induced by BK; this block was reversed by the NO donor DETANONOate. Vasoinhibins also prevented the BK-induced actin cytoskeleton redistribution, as did L-NAME. BK transiently decreased human RPE (ARPE-19) cell monolayer resistance, and this effect was blocked by vasoinhibins, L-NAME, and NAC. DETANONOate reverted the blocking effect of vasoinhibins. Similar to BK, the radical initiator Luperox induced a reduction in ARPE-19 cell monolayer resistance, which was prevented by vasoinhibins. These effects on RPE resistance coincided with actin cytoskeleton redistribution. Intravitreal injection of vasoinhibins reduced the levels of reactive oxygen species (ROS) in retinas of streptozotocin-induced diabetic rats, particularly in the RPE and capillary-containing layers. Thus, vasoinhibins reduce BRB permeability by targeting both its main inner and outer components through NO- and ROS-dependent pathways, offering potential treatment strategies against diabetic retinopathies. PMID:25368550

  13. Shape-dependence of the barrier for skyrmions on a two-lane racetrack

    NASA Astrophysics Data System (ADS)

    Müller, Jan

    2016-10-01

    Single magnetic skyrmions are localized whirls in the magnetization with an integer winding number. They have been observed on nano-meter scales up to room temperature in multilayer structures. Due to their small size, topological winding number, and their ability to be manipulated by extremely tiny forces, they are often called interesting candidates for future memory devices. The two-lane racetrack has to exhibit two lanes that are separated by an energy barrier. The information is then encoded in the position of a skyrmion which is located in one of these close-by lanes. The artificial barrier between the lanes can be created by an additional nanostrip on top of the track. Here we study the dependence of the potential barrier on the shape of the additional nanostrip, calculating the potentials for a rectangular, triangular, and parabolic cross section, as well as interpolations between the first two. We find that a narrow barrier is always repulsive and that the height of the potential strongly depends on the shape of the nanostrip, whereas the shape of the potential is more universal. We finally show that the shape-dependence is redundant for possible applications.

  14. Isothermal and cyclic oxidation of an air plasma-sprayed thermal barrier coating system

    SciTech Connect

    Haynes, J.A.; Ferber, M.K.; Porter, W.D.; Rigney, E.D.

    1996-08-01

    Thermogravimetric methods for evaluating bond coat oxidation in plasma-sprayed thermal barrier coating (TBC) systems were assessed by high-temperature testing of TBC systems with air plasma-sprayed (APS) Ni-22Cr-10Al-1Y bond coatings and yttria-stabilized zirconia top coatings. High-mass thermogravimetric analysis (at 1150{sup degrees}C) was used to measure bond coat oxidation kinetics. Furnace cycling was used to evaluate APS TBC durability. This paper describes the experimental methods and relative oxidation kinetics of the various specimen types. Characterization of the APS TBCs and their reaction products is discussed.

  15. Manganese Dependent Anaerobic Oxidation of Methane

    NASA Astrophysics Data System (ADS)

    Beal, E.; House, C.

    2007-12-01

    Understanding the anaerobic oxidation is not only important for understanding hydrocarbon degradation but it also important for understanding the global carbon cycle. The anaerobic oxidation of methane (AOM) is a large sink for methane consuming 5-20% of today's methane flux (Valentine and Reeburgh, 2000), yet the requirements for this process are not well understood. It has been suggested that no other electron acceptors other than sulfate can be used in the AOM (Nauhaus, 2005). However, our new data suggests that manganese, in the form of birnessite, can be used as an electron acceptor instead of sulfate (Beal et al., in prep). Methane seep sediment from the Eel River Basin, CA was incubated with methane, 13C-labeled methane, and carbon dioxide. Because the net result of the AOM is the production of carbon dioxide from methane, the rate of the AOM in each of the incubations can be determined by measuring the incorporation of 13C in the carbon dioxide. Using this method, it was found that cultures incubated with nitrate showed inhibition of the AOM, while cultures incubated with iron gave inconclusive results. The only positive results that were found for alternate electron acceptors are the incubations that were given manganese and no sulfate, which showed methane oxidation. Further, when more manganese was injected into these incubations, the rate of AOM increased. Preliminary analysis of the microbial population using terminal restriction fragment length polymorphism (TRFLP) targeting the mcr gene showed an unidentified organism in these cultures. Future work with TRFLP, as well as clone libraries, will help to identify the organisms responsible for this process. Nauhaus, K., 2005, Environmental regulation of the anaerobic oxidation of methane: a comparison of ANME-I and ANME-II communities: Environmental microbiology, v. 7, p. 98. Valentine, D.L., and Reeburgh, W.S., 2000, New perspectives on anaerobic methane oxidation: Environmental Microbiology, v. 2, p

  16. Tuning of barrier crossing time of a particle by time dependent magnetic field.

    PubMed

    Baura, Alendu; Ray, Somrita; Bag, Bidhan Chandra

    2013-06-28

    We have studied the effect of time dependent magnetic field on the barrier crossing dynamics of a charged particle. An interplay of the magnetic field induced electric field and the applied field reveals several interesting features. For slowly oscillating field the barrier crossing rate increases remarkably particularly at large amplitude of the field. For appreciably large frequency a generically distinct phenomenon appears by virtue of parametric resonance manifested in multiple peaks appearing in the variation of the mean first passage time as a function of the amplitude. The parametric resonance is more robust against the variation of amplitude of the oscillating field compared to the case of variation of frequency. The barrier crossing time of a particle can be tuned para-metrically by appropriate choice of amplitude and frequency of the oscillating magnetic field.

  17. Field-dependent energy barriers in Co/CoO core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Nieves, P.; Kechrakos, D.; Chubykalo-Fesenko, O.

    2016-02-01

    We perform atomistic modeling of Co/CoO nanoparticles with a diameter of a few nanometers and realistic values of the exchange and anisotropy parameters in order to study the field-dependent energy barriers under forward and backward reversal of the magnetization. The barriers are extracted from the constrained energy minimization using the integration of the Landau-Lifshitz-Gilbert equations and the Lagrange multiplier method. We show that the applied field and the interface exchange strength have opposite effects on the values of the energy barriers. In particular, while the backward (forward) energy barrier increases (decreases) linearly with the strength of the interface exchange coupling, it decreases (increases) almost quadratically with the applied magnetic field. Our results are in good agreement with the well-known Meiklejohn-Bean model of exchange bias, and allow us to analyze the limits of applicability of the macrospin approach to the study of energy barriers in core-shell Co/CoO nanoparticles.

  18. Mechanism of the development of a weakly alkaline barrier slurry without BTA and oxidizer

    NASA Astrophysics Data System (ADS)

    Xiaodong, Luan; Yuling, Liu; Xinhuan, Niu; Juan, Wang

    2015-07-01

    Controllable removal rate selectivity with various films (Cu, Ta, SiO2) is a challenging job in barrier CMP. H2O2 as an oxidizer and benzotriazole (BTA) as an inhibitor is considered to be an effective method in barrier CMP. Slurries that contain hydrogen peroxide have a very short shelf life because H2O2 is unstable and easily decomposed. BTA can cause post-CMP challenges, such as organic residue, toxicity and particle adhesion. We have been engaged in studying a weakly alkaline barrier slurry without oxidizer and benzotriazole. Based on these works, the objective of this paper is to discuss the mechanism of the development of the barrier slurry without oxidizer and benzotriazole by studying the effects of the different components (containing colloidal silica, FA/O complexing agent, pH of polishing solution and guanidine nitrate) on removal rate selectivity. The possible related polishing mechanism has also been proposed. Project supported by the Major National Science and Technology Special Projects (No. 2009ZX02308), the National Natural Science Foundation of Hebei Province, China (No. E2013202247), and the Department of Education-Funded Research Projects of Hebei Province, China (No. QN2014208).

  19. Methamphetamine-induced nitric oxide promotes vesicular transport in blood-brain barrier endothelial cells.

    PubMed

    Martins, Tânia; Burgoyne, Thomas; Kenny, Bridget-Ann; Hudson, Natalie; Futter, Clare E; Ambrósio, António F; Silva, Ana P; Greenwood, John; Turowski, Patric

    2013-02-01

    Methamphetamine's (METH) neurotoxicity is thought to be in part due to its ability to induce blood-brain barrier (BBB) dysfunction. Here, we investigated the effect of METH on barrier properties of cultured rat primary brain microvascular endothelial cells (BMVECs). Transendothelial flux doubled in response to METH, irrespective of the size of tracer used. At the same time, transendothelial electrical resistance was unchanged as was the ultrastructural appearance of inter-endothelial junctions and the distribution of key junction proteins, suggesting that METH promoted vesicular but not junctional transport. Indeed, METH significantly increased uptake of horseradish peroxidase into vesicular structures. METH also enhanced transendothelial migration of lymphocytes indicating that the endothelial barrier against both molecules and cells was compromised. Barrier breakdown was only observed in response to METH at low micromolar concentrations, with enhanced vesicular uptake peaking at 1 μM METH. The BMVEC response to METH also involved rapid activation of endothelial nitric oxide synthase and its inhibition abrogated METH-induced permeability and lymphocyte migration, indicating that nitric oxide was a key mediator of BBB disruption in response to METH. This study underlines the key role of nitric oxide in BBB function and describes a novel mechanism of drug-induced fluid-phase transcytosis at the BBB.

  20. Impedance Analysis of 7YSZ Thermal Barrier Coatings During High-Temperature Oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Wen-Long; Liu, Min; Zhang, Ji-Fu

    2016-12-01

    ZrO2-7 wt.%Y2O3 (7YSZ) thermal barrier coatings (TBCs) were prepared by atmospheric plasma spraying. High-temperature oxidation of 7YSZ TBCs was accomplished at 950 °C and characterized by impedance spectroscopy and scanning electron microscopy with energy-dispersive spectrometry. The results indicated that the thermally grown oxide (TGO) mainly contained alumina. The increase of the thickness of the TGO layer appeared to follow a parabolic law. Impedance analysis demonstrated that the resistance of the TGO increased with increasing oxidation time, also following a parabolic law, and that characterization of the TGO thickness based on fitting an equivalent circuit to its measured resistance is feasible. The YSZ grain-boundary resistance increased due to increasing cracks within the coating for oxidation time less than 50 h. However, beyond 150 h, the YSZ grain-boundary resistance slightly decreased, mainly due to sintering of the coating during the oxidation process.

  1. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions

    NASA Astrophysics Data System (ADS)

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-07-01

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits.

  2. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions.

    PubMed

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-07-12

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits.

  3. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions

    PubMed Central

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-01-01

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits. PMID:27403611

  4. Anaerobic Nitrate-Dependent Metal Bio-Oxidation

    NASA Astrophysics Data System (ADS)

    Weber, K.; Knox, T.; Achenbach, L. A.; Coates, J. D.

    2007-12-01

    Direct biological oxidation of reduced metals (Fe(II) and U(IV)) coupled to nitrate reduction at circumneutral pH under anaerobic conditions has been recognized in several environments as well as pure culture. Several phylogentically diverse mesophilic bacteria have been described as capable of anaerobic, nitrate-dependent Fe(II) oxidation (NFOx). Our recent identification of a freshwater mesophilic, lithoautotroph, Ferrutens nitratireducens strain 2002, capable of growth through NFOx presents an opportunity to further study metal bio- oxidation. Continuing physiological studies revealed that in addition to Fe(II) oxidation, strain 2002 is capable of oxidizing U(IV) (4 μM) in washed cell suspensions with nitrate serving as the electron acceptor. Pasteurized cultures exhibited abiotic oxidation of 2 μM U(IV). Under growth conditions, strain 2002 catalyzed the oxidation of 12 μM U(IV) within a two week period. Cultures amended with sodium azide, an electron transport inhibitor, demonstrated limited oxidation (7 μM) similar to pasteurized cultures, supporting the direct role of electron transport in U(IV) bio-oxidation. The oxidation of U(IV) coupled denitrification at circumneutral pH would yield enough energy to support anaerobic microbial growth (ΔG°'= -460.36 kJ/mole). It is currently unknown whether or not strain 2002 can couple this metabolism to growth. The growth of F. nitratireducens strain 2002 utilizing Fe(II) as the sole electron donor was previously demonstrated. The amount of U(IV) (~12 μM) that strain 2002 oxidized under similar autotrophic growth conditions yields 0.0019 kJ, enough energy for the generation of ATP (5.3 x 10-20 kJ ATP-1), but not enough energy for cell replication as calculated for nitrate-dependent Fe(II) oxidizing conditions (0.096 kJ) assuming a similar metabolism. In addition to F. nitratireducens strain 2002, a nitrate-dependent Fe(II) oxidizing bacterium isolated from U contaminated groundwater, Diaphorobacter sp. strain

  5. Reducing ac losses of Bi(2223) multifilamentary tapes by oxide barriers

    NASA Astrophysics Data System (ADS)

    Huang, Y. B.; Flükiger, R.

    1998-01-01

    A new type of sheath material, consisting of a thin layer BaZrO 3 around each filament, has been used to fabricate Bi(2223) multifilamentary tapes. The transverse resistivity is enhanced by a factor of 10, thus leading to a significant reduction of ac coupling losses in Bi(2223) multifilamentary tapes. The electric decoupling effect of these barriers is clearly demonstrated by “magnetic length scale” and Hall sensor magnetisation experiments. Moreover, it is possible to twist these tapes with a pitch length of 2 cm, thus yielding an even higher decoupling effect without deterioration of the transport properties. The uniformity of filament size and barrier layer thickness have been improved by a modified PIT method using four-roll deformation. The critical current density of these Bi(2223) tapes with BaZrO 3 oxide barriers so far reaches 15 kA/cm 2 (77 K, 0 T).

  6. Zirconia and Pyrochlore Oxides for Thermal Barrier Coatings in Gas Turbine Engines

    DOE PAGES

    Fergus, Jeffrey W.

    2014-04-12

    One of the important applications of yttria stabilized zirconia is as a thermal barrier coating for gas turbine engines. While yttria stabilized zirconia performs well in this function, the need for increased operating temperatures to achieve higher energy conversion efficiencies, requires the development of improved materials. To meet this challenge, some rare-earth zirconates that form the cubic fluorite derived pyrochlore structure are being developed for use in thermal barrier coatings due to their low thermal conductivity, excellent chemical stability and other suitable properties. In this paper, the thermal conductivities of current and prospective oxides for use in thermal barrier coatingsmore » are reviewed. The factors affecting the variations and differences in the thermal conductivities and the degradation behaviors of these materials are discussed.« less

  7. Zirconia and Pyrochlore Oxides for Thermal Barrier Coatings in Gas Turbine Engines

    SciTech Connect

    Fergus, Jeffrey W.

    2014-04-12

    One of the important applications of yttria stabilized zirconia is as a thermal barrier coating for gas turbine engines. While yttria stabilized zirconia performs well in this function, the need for increased operating temperatures to achieve higher energy conversion efficiencies, requires the development of improved materials. To meet this challenge, some rare-earth zirconates that form the cubic fluorite derived pyrochlore structure are being developed for use in thermal barrier coatings due to their low thermal conductivity, excellent chemical stability and other suitable properties. In this paper, the thermal conductivities of current and prospective oxides for use in thermal barrier coatings are reviewed. The factors affecting the variations and differences in the thermal conductivities and the degradation behaviors of these materials are discussed.

  8. Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

    NASA Astrophysics Data System (ADS)

    Mahmoodlu, Mojtaba G.; Hassanizadeh, S. Majid; Hartog, Niels; Raoof, Amir

    2014-08-01

    The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw = 0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

  9. Real-time oxide evolution of copper protected by graphene and boron nitride barriers

    NASA Astrophysics Data System (ADS)

    Galbiati, M.; Stoot, A. C.; MacKenzie, D. M. A.; Bøggild, P.; Camilli, L.

    2017-01-01

    Applying protective or barrier layers to isolate a target item from the environment is a common approach to prevent or delay its degradation. The impermeability of two-dimensional materials such as graphene and hexagonal boron nitride (hBN) has generated a great deal of interest in corrosion and material science. Owing to their different electronic properties (graphene is a semimetal, whereas hBN is a wide-bandgap insulator), their protection behaviour is distinctly different. Here we investigate the performance of graphene and hBN as barrier coatings applied on copper substrates through a real-time study in two different oxidative conditions. Our findings show that the evolution of the copper oxidation is remarkably different for the two coating materials.

  10. Thin Oxides as a Cu Diffusion Barrier for NIF Be Ablator Capsules

    DOE PAGES

    Youngblood, Kelly P.; Huang, H.; Xu, H. W.; ...

    2013-03-01

    The NIF point design uses a five-layer capsule to modify the X-ray absorption in order to achieve optimized shock timing. A stepped copper dopant design defines the layer structure. The production of the capsule involves pyrolysis to remove the inner plastic mandrel. Copper atoms diffuse radially and azimuthally throughout the capsule during pyrolysis. This diffusion significantly diminishes the capsule performance during implosion. Thermal and coated oxide barrier layers employed between layers mitigate the diffusion of copper during the mandrel removal process. The copper atoms do not diffuse through this barrier during pyrolysis. A capsule fabrication method that produces a capsulemore » with a thin oxide layer will be discussed.« less

  11. Real-time oxide evolution of copper protected by graphene and boron nitride barriers

    PubMed Central

    Galbiati, M.; Stoot, A. C.; Mackenzie, D. M. A.; Bøggild, P.; Camilli, L.

    2017-01-01

    Applying protective or barrier layers to isolate a target item from the environment is a common approach to prevent or delay its degradation. The impermeability of two-dimensional materials such as graphene and hexagonal boron nitride (hBN) has generated a great deal of interest in corrosion and material science. Owing to their different electronic properties (graphene is a semimetal, whereas hBN is a wide-bandgap insulator), their protection behaviour is distinctly different. Here we investigate the performance of graphene and hBN as barrier coatings applied on copper substrates through a real-time study in two different oxidative conditions. Our findings show that the evolution of the copper oxidation is remarkably different for the two coating materials. PMID:28067249

  12. Physicochemical Factors that Affect Metal and Metal Oxide Nanoparticle Passage Across Epithelial Barriers

    PubMed Central

    Elder, Alison; Vidyasagar, Sadasivan; DeLouise, Lisa

    2014-01-01

    The diversity of nanomaterials in terms of size, shape, and surface chemistry poses a challenge to those who are trying to characterize the human health and environmental risks associated with incidental and unintentional exposures. There are numerous products that are already commercially available that contain solid metal and metal oxide nanoparticles, either embedded in a matrix or in solution. Exposure assessments for these products are often incomplete or difficult due to technological challenges associated with detection and quantitation of nanoparticles in gaseous or liquid carriers. The main focus of recent research has been on hazard identification. However, risk is a product of hazard and exposure, and one significant knowledge gap is that of the target organ dose following in vivo exposures. In order to reach target organs, nanoparticles must first breech the protective barriers of the respiratory tract, gastrointestinal tract, or skin. The fate of those nanoparticles that reach physiological barriers is in large part determined by the properties of the particles and the barriers themselves. This article reviews the physiological properties of the lung, gut, and skin epithelia, the physicochemical properties of metal and metal oxide nanoparticles that are likely to affect their ability to breech epithelial barriers, and what is known about their fate following in vivo exposures. PMID:20049809

  13. GRP78 is a novel receptor initiating a vascular barrier protective response to oxidized phospholipids.

    PubMed

    Birukova, Anna A; Singleton, Patrick A; Gawlak, Grzegorz; Tian, Xinyong; Mirzapoiazova, Tamara; Mambetsariev, Bolot; Dubrovskyi, Oleksii; Oskolkova, Olga V; Bochkov, Valery N; Birukov, Konstantin G

    2014-07-01

    Vascular integrity and the maintenance of blood vessel continuity are fundamental features of the circulatory system maintained through endothelial cell-cell junctions. Defects in the endothelial barrier become an initiating factor in several pathologies, including ischemia/reperfusion, tumor angiogenesis, pulmonary edema, sepsis, and acute lung injury. Better understanding of mechanisms stimulating endothelial barrier enhancement may provide novel therapeutic strategies. We previously reported that oxidized phospholipids (oxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine [OxPAPC]) promote endothelial cell (EC) barrier enhancement both in vitro and in vivo. This study examines the initiating mechanistic events triggered by OxPAPC to increase vascular integrity. Our data demonstrate that OxPAPC directly binds the cell membrane-localized chaperone protein, GRP78, associated with its cofactor, HTJ-1. OxPAPC binding to plasma membrane-localized GRP78 leads to GRP78 trafficking to caveolin-enriched microdomains (CEMs) on the cell surface and consequent activation of sphingosine 1-phosphate receptor 1, Src and Fyn tyrosine kinases, and Rac1 GTPase, processes essential for cytoskeletal reorganization and EC barrier enhancement. Using animal models of acute lung injury with vascular hyperpermeability, we observed that HTJ-1 knockdown blocked OxPAPC protection from interleukin-6 and ventilator-induced lung injury. Our data indicate for the first time an essential role of GRP78 and HTJ-1 in OxPAPC-mediated CEM dynamics and enhancement of vascular integrity.

  14. Ultrasonic characterization of thermally grown oxide in thermal barrier coating by reflection coefficient amplitude spectrum.

    PubMed

    Ma, Zhiyuan; Zhao, Yang; Luo, Zhongbing; Lin, Li

    2014-04-01

    The thermally grown oxide (TGO) growth at the interface of ceramic coating/bond coating in thermal barrier coatings (TBCs) was evaluated by ultrasonic reflection coefficient amplitude spectrum (URCAS). A theoretical analysis was performed about the influence of acoustic impedance match relationship between the ceramic coating and its adjacent media on URCAS. The immersion ultrasonic narrow pulse echo method was carried out on the TBC specimen before and after oxidation under 1050°C×1h for 15cycles. The resonant peaks of URCAS obtained before and after oxidation showed that TGO which generated between the ceramic coating and bond coating due to the oxidation, changed the acoustic impedance match between the ceramic coating and its adjacent media. This method is able to nondestructively characterize the generation of TGO in TBCs, and is important to practical engineering application.

  15. Ultrathin epitaxial barrier layer to avoid thermally induced phase transformation in oxide heterostructures

    SciTech Connect

    Baek, David J.; Lu, Di; Hikita, Yasuyuki; Hwang, Harold Y.; Kourkoutis, Lena F.

    2016-12-22

    Incorporating oxides with radically different physical and chemical properties into heterostructures offers tantalizing possibilities to derive new functions and structures. Recently, we have fabricated freestanding 2D oxide membranes using the water-soluble perovskite Sr3Al2O6 as a sacrificial buffer layer. Here, with atomic-resolution spectroscopic imaging, we observe that direct growth of oxide thin films on Sr3Al2O6 can cause complete phase transformation of the buffer layer, rendering it water-insoluble. More importantly, we demonstrate that an ultrathin SrTiO3 layer can be employed as an effective barrier to preserve Sr3Al2O6 during subsequent growth, thus allowing its integration in a wider range of oxide heterostructures.

  16. Ultrathin epitaxial barrier layer to avoid thermally induced phase transformation in oxide heterostructures

    DOE PAGES

    Baek, David J.; Lu, Di; Hikita, Yasuyuki; ...

    2016-12-22

    Incorporating oxides with radically different physical and chemical properties into heterostructures offers tantalizing possibilities to derive new functions and structures. Recently, we have fabricated freestanding 2D oxide membranes using the water-soluble perovskite Sr3Al2O6 as a sacrificial buffer layer. Here, with atomic-resolution spectroscopic imaging, we observe that direct growth of oxide thin films on Sr3Al2O6 can cause complete phase transformation of the buffer layer, rendering it water-insoluble. More importantly, we demonstrate that an ultrathin SrTiO3 layer can be employed as an effective barrier to preserve Sr3Al2O6 during subsequent growth, thus allowing its integration in a wider range of oxide heterostructures.

  17. Control of the anodic aluminum oxide barrier layer opening process by wet chemical etching.

    PubMed

    Han, Catherine Y; Willing, Gerold A; Xiao, Zhili; Wang, H Hau

    2007-01-30

    In this work, it has been shown that, through a highly controlled process, the chemical etching of the anodic aluminum oxide membrane barrier layer can be performed in such a way as to achieve nanometer-scale control of the pore opening. As the barrier layer is etched away, subtle differences revealed through AFM phase imaging in the alumina composition in the barrier layer give rise to a unique pattern of hexagonal walls surrounding each of the barrier layer domes. These nanostructures observed in both topography and phase images can be understood as differences in the oxalate anion contaminated alumina versus pure alumina. This information bears significant implication for catalysis, template synthesis, and chemical sensing applications. From the pore opening etching studies, the etching rate of the barrier layer (1.3 nm/min) is higher than that of the inner cell wall (0.93 nm/min), both of which are higher than the etching rate of pure alumina layer (0.5-0.17 nm/min). The established etching rates together with the etching temperature allow one to control the pore diameter systematically from 10 to 95 nm.

  18. Furnace Cyclic Oxidation Behavior of Multi-Component Low Conductivity Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dong-Ming; Nesbitt, James A.; Barrett, Charles A.; McCue, Terry R.; Miller, Robert A.

    2004-01-01

    Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to further increase engine operating temperatures and reduce cooling, thus helping achieve future engine low emission, high efficiency and improved reliability goals. Advanced multi-component zirconia-based thermal barrier coatings are being developed using an oxide defect clustering design approach to achieve the required coating low thermal conductivity and high temperature stability. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of the candidate coating materials was conducted using conventional furnace cyclic oxidation tests. In this paper, furnace cyclic oxidation behavior of plasma-sprayed zirconia-based defect cluster thermal barrier coatings was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied using scanning electron microscopy (SEM) combined with X-ray diffraction (XRD) phase analysis after the furnace tests. The coating cyclic lifetime is also discussed in relation to coating processing, phase structures, dopant concentration, and other thermo-physical properties.

  19. Vitamin C crosses the blood-brain barrier in the oxidized form through the glucose transporters.

    PubMed Central

    Agus, D B; Gambhir, S S; Pardridge, W M; Spielholz, C; Baselga, J; Vera, J C; Golde, D W

    1997-01-01

    Vitamin C concentrations in the brain exceed those in blood by 10-fold. In both tissues, the vitamin is present primarily in the reduced form, ascorbic acid. We identified the chemical form of vitamin C that readily crosses the blood-brain barrier, and the mechanism of this process. Ascorbic acid was not able to cross the blood-brain barrier in our studies. In contrast, the oxidized form of vitamin C, dehydroascorbic acid (oxidized ascorbic acid), readily entered the brain and was retained in the brain tissue in the form of ascorbic acid. Transport of dehydroascorbic acid into the brain was inhibited by d-glucose, but not by l-glucose. The facilitative glucose transporter, GLUT1, is expressed on endothelial cells at the blood-brain barrier, and is responsible for glucose entry into the brain. This study provides evidence showing that GLUT1 also transports dehydroascorbic acid into the brain. The findings define the transport of dehydroascorbic acid by GLUT1 as a mechanism by which the brain acquires vitamin C, and point to the oxidation of ascorbic acid as a potentially important regulatory step in accumulation of the vitamin by the brain. These results have implications for increasing antioxidant potential in the central nervous system. PMID:9389750

  20. Effects of intrinsic degrees of freedom in enhancement of sub-barrier fusion excitation function data and energy-dependent one-dimensional barrier penetration model

    NASA Astrophysics Data System (ADS)

    Gautam, M. S.

    2016-03-01

    We have analyzed the role of barrier modification effects (barrier height, barrier position, barrier curvature) introduced due to the energy-dependent Woods-Saxon potential model (EDWSP model) and the coupled channel model on the sub-barrier fusion dynamics of {}_{16}^{32,36} {{S}} + {}_{40}^{90,96} {{Zr}} reactions. The influence of inelastic surface excitations of colliding pairs and multi-neutron transfer channels is found to be a dominant mode of couplings. The coupling of relative motion of colliding nuclei to these dominant intrinsic degrees of freedom leads to a substantially large fusion enhancement at below-barrier energies over the expectations of one-dimensional barrier penetration model. The coupled channel calculations based upon static Woods-Saxon potential must include the internal nuclear structure degrees of freedom of colliding nuclei for complete description of experimental data. On the other hand, theoretical calculations based upon the EDWSP model along with Wong formula provide a complete description of sub-barrier fusion enhancement of various heavy-ion fusion reactions. In EDWSP model calculations, significantly larger values of diffuseness parameter ranging from a = 0.98 fm to a = 0.85 fm are required to address the observed sub-barrier fusion enhancement of {}_{16}^{32,36} {{S}} + {}_{40}^{90,96} {{Zr}} reactions. Furthermore, within the context of EDWSP model, it is possible to achieve an agreement with the experimental fusion cross-sectional data within 10 %. For four heavy-ion fusion reactions, only at 4 fusion data points out of 90 fusion data points deviates exceeding 5 %, while 86 fusion data points lie within 5 % and hence the EDWSP model is able to account the above-barrier portion of the fusion cross-sectional data within 5 % with a probability greater than 90 %.

  1. Sub-barrier fusion excitation function data and energy dependent Woods-Saxon potential

    NASA Astrophysics Data System (ADS)

    Gautam, Manjeet Singh

    2016-07-01

    This paper analyzed the role of intrinsic degrees of freedom of colliding nuclei in the enhancement of sub-barrier fusion cross-section data of various heavy ion fusion reactions. The influences of inelastic surface vibrations of colliding pairs are found to be dominant and their couplings result in the significantly larger fusion enhancement over the predictions of the one dimensional barrier penetration model at sub-barrier energies. The theoretical calculations are performed by using energy dependent Woods-Saxon potential model (EDWSP model) in conjunction with the one dimensional Wong formula. The effects of dominant intrinsic channels are entertained within framework of the coupled channel calculations obtained by using the code CCFULL. It is quite interesting to note that the energy dependence in Woods-Saxon potential simulates the effects of inelastic surface vibrational states of reactants wherein significantly larger value of diffuseness parameter ranging from a = 0.85 fm to a = 0.95 fm is required to address the observed fusion excitation function data of the various heavy ion fusion reactions.

  2. Master equation approach to time-dependent escape rate over a periodically oscillating barrier.

    PubMed

    Wang, Xin-Xin; Bao, Jing-Dong

    2011-01-01

    We propose a master equation approach to investigate the transition function and the escape dynamics of a general damping particle in a metastable potential. The transition function in the master equation is obtained analytically from the Langevin dynamics. We apply it to the oscillating barrier problem, in which the potential is structured by a harmonic potential smoothly linking with an inverse harmonic one, and thus both the barrier height and the curvature of potential change periodically with time. We use a Monte Carlo method to simulate the master equation and then calculate a time-dependent escape rate. This can decrease the coarse grain and save more computing time in comparison with the Langevin simulation. Our result has shown that there is a resonant activation phenomenon for the escape rate in the underdamped case.

  3. Environmental degradation of oxidation resistant and thermal barrier coatings for fuel-flexible gas turbine applications

    NASA Astrophysics Data System (ADS)

    Mohan, Prabhakar

    The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O 5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO 4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O 3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na 2SO4 and a Na2SO4 + V2

  4. Nonthermal dielectric-barrier discharge plasma-induced inactivation involves oxidative DNA damage and membrane lipid peroxidation in Escherichia coli.

    PubMed

    Joshi, Suresh G; Cooper, Moogega; Yost, Adam; Paff, Michelle; Ercan, Utku K; Fridman, Gregory; Friedman, Gary; Fridman, Alexander; Brooks, Ari D

    2011-03-01

    Oxidative stress leads to membrane lipid peroxidation, which yields products causing variable degrees of detrimental oxidative modifications in cells. Reactive oxygen species (ROS) are the key regulators in this process and induce lipid peroxidation in Escherichia coli. Application of nonthermal (cold) plasma is increasingly used for inactivation of surface contaminants. Recently, we reported a successful application of nonthermal plasma, using a floating-electrode dielectric-barrier discharge (FE-DBD) technique for rapid inactivation of bacterial contaminants in normal atmospheric air (S. G. Joshi et al., Am. J. Infect. Control 38:293-301, 2010). In the present report, we demonstrate that FE-DBD plasma-mediated inactivation involves membrane lipid peroxidation in E. coli. Dose-dependent ROS, such as singlet oxygen and hydrogen peroxide-like species generated during plasma-induced oxidative stress, were responsible for membrane lipid peroxidation, and ROS scavengers, such as α-tocopherol (vitamin E), were able to significantly inhibit the extent of lipid peroxidation and oxidative DNA damage. These findings indicate that this is a major mechanism involved in FE-DBD plasma-mediated inactivation of bacteria.

  5. Akt-mediated transactivation of the S1P1 receptor in caveolin-enriched microdomains regulates endothelial barrier enhancement by oxidized phospholipids.

    PubMed

    Singleton, Patrick A; Chatchavalvanich, Santipongse; Fu, Panfeng; Xing, Junjie; Birukova, Anna A; Fortune, Jennifer A; Klibanov, Alexander M; Garcia, Joe G N; Birukov, Konstantin G

    2009-04-24

    Endothelial cell (EC) barrier dysfunction results in increased vascular permeability, leading to increased mass transport across the vessel wall and leukocyte extravasation, the key mechanisms in pathogenesis of tissue inflammation and edema. We have previously demonstrated that OxPAPC (oxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine) significantly enhances vascular endothelial barrier properties in vitro and in vivo and attenuates endothelial hyperpermeability induced by inflammatory and edemagenic agents via Rac and Cdc42 GTPase dependent mechanisms. These findings suggested potential important therapeutic value of barrier-protective oxidized phospholipids. In this study, we examined involvement of signaling complexes associated with caveolin-enriched microdomains (CEMs) in barrier-protective responses of human pulmonary ECs to OxPAPC. Immunoblotting from OxPAPC-treated ECs revealed OxPAPC-mediated rapid recruitment (5 minutes) to CEMs of the sphingosine 1-phosphate receptor (S1P(1)), the serine/threonine kinase Akt, and the Rac1 guanine nucleotide exchange factor Tiam1 and phosphorylation of caveolin-1, indicative of signaling activation in CEMs. Abolishing CEM formation (methyl-beta-cyclodextrin) blocked OxPAPC-mediated Rac1 activation, cytoskeletal reorganization, and EC barrier enhancement. Silencing (small interfering RNA) Akt expression blocked OxPAPC-mediated S1P(1) activation (threonine phosphorylation), whereas silencing S1P(1) receptor expression blocked OxPAPC-mediated Tiam1 recruitment to CEMs, Rac1 activation, and EC barrier enhancement. To confirm our in vitro results in an in vivo murine model of acute lung injury with pulmonary vascular hyperpermeability, we observed that selective lung silencing of caveolin-1 or S1P(1) receptor expression blocked OxPAPC-mediated protection from ventilator-induced lung injury. Taken together, these results suggest Akt-dependent transactivation of S1P(1) within CEMs is important for Ox

  6. The burnup dependence of light water reactor spent fuel oxidation

    SciTech Connect

    Hanson, B.D.

    1998-07-01

    Over the temperature range of interest for dry storage or for placement of spent fuel in a permanent repository under the conditions now being considered, UO{sub 2} is thermodynamically unstable with respect to oxidation to higher oxides. The multiple valence states of uranium allow for the accommodation of interstitial oxygen atoms in the fuel matrix. A variety of stoichiometric and nonstoichiometric phases is therefore possible as the fuel oxidizers from UO{sub 2} to higher oxides. The oxidation of UO{sub 2} has been studied extensively for over 40 years. It has been shown that spent fuel and unirradiated UO{sub 2} oxidize via different mechanisms and at different rates. The oxidation of LWR spent fuel from UO{sub 2} to UO{sub 2.4} was studied previously and is reasonably well understood. The study presented here was initiated to determine the mechanism and rate of oxidation from UO{sub 2.4} to higher oxides. During the early stages of this work, a large variability in the oxidation behavior of samples oxidized under nearly identical conditions was found. Based on previous work on the effect of dopants on UO{sub 2} oxidation and this initial variability, it was hypothesized that the substitution of fission product and actinide impurities for uranium atoms in the spent fuel matrix was the cause of the variable oxidation behavior. Since the impurity concentration is roughly proportional to the burnup of a specimen, the oxidation behavior of spent fuel was expected to be a function of both temperature and burnup. This report (1) summarizes the previous oxidation work for both unirradiated UO{sub 2} and spent fuel (Section 2.2) and presents the theoretical basis for the burnup (i.e., impurity concentration) dependence of the rate of oxidation (Sections 2.3, 2.4, and 2.5), (2) describes the experimental approach (Section 3) and results (Section 4) for the current oxidation tests on spent fuel, and (3) establishes a simple model to determine the activation energies

  7. Gas Barrier and Separation Behavior of Graphene Oxide Nanobrick Wall Thin Films

    NASA Astrophysics Data System (ADS)

    Grunlan, Jaime

    2015-03-01

    In many cases, electronics packaging requires electrical conductivity and barrier to oxygen, even under humid conditions. These two properties have simultaneously been realized through the use of surfactant-free aqueous layer-by-layer (LbL) processing, in the form of a polymer composite nanocoating. By layering graphene oxide (GO) with polyethyleneimine (PEI), a ``nano brick wall'' structure has been created, imparting gas barrier properties to the film. Reducing the graphene oxide with a thermal treatment further produces high oxygen barrier in humid conditions and imparts high electrical conductivity (σ ~ 1750 S/m). These thin films (<400 nm) are flexible relative traditional conductive thin films (e.g. ITO), and processing occurs under ambient conditions with water as the only solvent. Additionally, these PEI/GO thin films exhibit H2/CO2 selectivity (>300), making them interesting for gas purification membranes. The flexible nature of the aforementioned thin films, along with their excellent combination of transport properties, make them ideal candidates for use in a broad range of electronics and other packaging applications.

  8. Nitric Oxide and Airway Epithelial Barrier Function: Regulation of Tight Junction Proteins and Epithelial Permeability

    PubMed Central

    Olson, Nels; Greul, Anne-Katrin; Hristova, Milena; Bove, Peter F.; Kasahara, David I.; van der Vliet, Albert

    2008-01-01

    Acute airway inflammation is associated with enhanced production of nitric oxide (NO•) and altered airway epithelial barrier function, suggesting a role of NO• or its metabolites in epithelial permeability. While high concentrations of S-nitrosothiols disrupted transepithelial resistance (TER) and increased permeability in 16HBE14o- cells, no significant barrier disruption was observed by NONOates, in spite of altered distribution and expression of some TJ proteins. Barrier disruption of mouse tracheal epithelial (MTE) cell monolayers in response to inflammatory cytokines was independent of NOS2, based on similar effects in MTE cells from NOS2-/- mice and a lack of effect of the NOS2-inhibitor 1400W. Cell pre-incubation with LPS protected MTE cells from TER loss and increased permeability by H2O2, which was independent of NOS2. However, NOS2 was found to contribute to epithelial wound repair and TER recovery after mechanical injury. Overall, our results demonstrate that epithelial NOS2 is not responsible for epithelial barrier dysfunction during inflammation, but may contribute to restoration of epithelial integrity. PMID:19100237

  9. Protein kinase C-mediated endothelial barrier regulation is caveolin-1-dependent.

    PubMed

    Waschke, Jens; Golenhofen, Nikola; Kurzchalia, Teymuras V; Drenckhahn, Detlev

    2006-07-01

    Protein kinase C (PKC) is activated in response to various inflammatory mediators and contributes significantly to the endothelial barrier breakdown. However, the mechanisms underlying PKC-mediated permeability regulation are not well understood. We prepared microvascular myocardial endothelial cells from both wild-type (WT) and caveolin-1-deficient mice. Activation of PKC by phorbol myristate acetate (PMA) (100 nM) for 30 min induced intercellular gap formation and fragmentation of VE-cadherin immunoreactivity in WT but not in caveolin-1-deficient monolayers. To test the effect of PKC activation on VE-cadherin-mediated adhesion, we allowed VE-cadherin-coated microbeads to bind to the endothelial cell surface and probed their adhesion by laser tweezers. PMA significantly reduced bead binding to 78+/-6% of controls in WT endothelial cells without any effect in caveolin-1-deficient cells. In WT cells, PMA caused an 86+/-18% increase in FITC-dextran permeability whereas no increase in permeability was observed in caveolin-1-deficient monolayers. Inhibition of PKC by staurosporine (50 nM, 30 min) did not affect barrier functions in both WT and caveolin-1-deficient MyEnd cells. Theses data indicate that PKC activation reduces endothelial barrier functions at least in part by the reduction of VE-cadherin-mediated adhesion and demonstrate that PKC-mediated permeability regulation depends on caveolin-1.

  10. Effect of shot peening on the oxidation behavior of thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Karaoglanli, Abdullah Cahit; Doleker, Kadir Mert; Demirel, Bilal; Turk, Ahmet; Varol, Remzi

    2015-11-01

    A conventional thermal barrier coating (TBC) system is made up of a multilayered coating system that comprises a metallic bond coat including oxidation-resistant MCrAlY and a thermally insulating ceramic top coat including yttria stabilized zirconia (YSZ). In this study, in order to improve the oxidation behavior in conventionally produced TBC systems, shot peening process is applied for modification of surface layer structure of atmospheric plasma spray (APS) bond coats. The oxidation behavior of TBCs, produced by the APS process and subjected to shot peening, was investigated. Oxidation tests were performed under isothermal conditions at 1000 °C for different time periods. The coatings produced by the APS process include high porosity and oxide content due to atmospheric production conditions as well as exposure to very high temperature. In this study, the coatings, produced by the APS process, subsequently subjected to shot-peening, were compared with the ones which were not shot peened. Following the application of the shot peening process, a dense structure is obtained due to the plastic deformation effect in the metallic bond coating structure at a certain distance from the surface. To this end, the effects of the shot-peening on the high temperature oxidation behavior of the coatings are investigated and evaluated.

  11. High thermal stability of magnetic tunnel junctions with oxide diffusion barrier layers

    NASA Astrophysics Data System (ADS)

    Fukumoto, Yoshiyuki; Shimura, Ken-ichi; Kamijo, Atsushi; Tahara, Shuichi; Yoda, Hiroaki

    2004-01-01

    We developed two types of magnetic tunnel junctions (MTJs) that showed high thermal stability. One is a PtMn exchange-biased spin-valve MTJ with a CoFe/Al-oxide (AlOx)/NiFe free layer and a CoFeTaOx/CoFe pinned layer, and the other is a pseudo-spin-valve (PSV) MTJ with a CoFe/AlOx/NiFe soft layer, where AlOx and CoFeTaOx act as barriers for Ni and Mn diffusion toward the tunnel barrier, respectively. After 390 °C-1H annealing, the PSV MTJs maintained 28% and the SV MTJs 39% of tunnel magnetoresistance. Transmission electron microscopy observation of the SV MTJs after 380 °C-1H annealing revealed that the migrated Mn atoms were trapped at the CoFeTaOx layer.

  12. Targeting Transporters: Promoting Blood-Brain Barrier Repair in Response to Oxidative Stress Injury

    PubMed Central

    Ronaldson, Patrick T.; Davis, Thomas P.

    2015-01-01

    The blood-brain barrier (BBB) is a physical and biochemical barrier that precisely regulates the ability of endogenous and exogenous substances to accumulate within brain tissue. It possesses structural and biochemical features (i.e., tight junction and adherens junction protein complexes, influx and efflux transporters) that work in concert to control solute permeation. Oxidative stress, a critical component of several diseases including cerebral hypoxia/ischemia and peripheral inflammatory pain, can cause considerable injury to the BBB and lead to significant CNS pathology. This suggests a critical need for novel therapeutic approaches that can protect the BBB in diseases with an oxidative stress component. Recent studies have identified molecular targets (i.e., endogenous transporters, intracellular signaling systems) that can be exploited for optimization of endothelial drug delivery or for control of transport of endogenous substrates such as the antioxidant glutathione (GSH). In particular, targeting transporters offers a unique approach to protect BBB integrity by promoting repair of cell-cell interactions at the level of the brain microvascular endothelium. This review summarizes current knowledge in this area and emphasizes those targets that present considerable opportunity for providing BBB protection and/or promoting BBB repair in the setting of oxidative stress. PMID:25796436

  13. Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G.; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

    2016-05-01

    Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites.Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical

  14. Time dependent semiclassical tunneling through one dimensional barriers using only real valued trajectories

    SciTech Connect

    Herman, Michael F.

    2015-10-28

    The time independent semiclassical treatment of barrier tunneling has been understood for a very long time. Several semiclassical approaches to time dependent tunneling through barriers have also been presented. These typically involve trajectories for which the position variable is a complex function of time. In this paper, a method is presented that uses only real valued trajectories, thus avoiding the complications that can arise when complex trajectories are employed. This is accomplished by expressing the time dependent wave packet as an integration over momentum. The action function in the exponent in this expression is expanded to second order in the momentum. The expansion is around the momentum, p{sub 0{sup *}}, at which the derivative of the real part of the action is zero. The resulting Gaussian integral is then taken. The stationary phase approximation requires that the derivative of the full action is zero at the expansion point, and this leads to a complex initial momentum and complex tunneling trajectories. The “pseudo-stationary phase” approximation employed in this work results in real values for the initial momentum and real valued trajectories. The transmission probabilities obtained are found to be in good agreement with exact quantum results.

  15. Fe nanoparticles on ZnSe: Reversible temperature dependence of the surface barrier potential

    NASA Astrophysics Data System (ADS)

    Cantoni, M.; Bertacco, R.; Brambilla, A.; Finazzi, M.; Duò, L.; Ciccacci, F.; Verdini, A.; Floreano, L.; Morgante, A.; Passoni, M.; Casari, C. S.; Li Bassi, A.

    2012-04-01

    The Fe growth on ZnSe(001) takes place via the initial formation of superparamagnetic nano-islands that subsequently coalesce, giving rise to a continuous film for a nominal thickness of 8 Fe monolayers. For a very low Fe coverage (2 Fe monolayers), we show that the surface barrier potential (i.e. the barrier potential seen by electrons incident on the surface), measured by absorbed current spectroscopy, attains very large values (6.9 eV at room temperature) and dramatically changes as a function of temperature, with an increase of ˜1.5 eV from room temperature down to 130 K, largely exceeding similar changes observed in both thin films and nanoparticles. This phenomenon disappears as the thickness increases and is fully reversible with temperature. Nonequilibrium phenomena due to the experimental conditions are present, but are not able to explain the observed data. Inverse photoemission, core level photoemission, x-ray photoemission diffraction, and scanning tunneling microscopy are employed in order to find temperature-dependent properties of the Fe islands: while only minor changes as a function of temperature are present in the electronic band structure, the Fe crystal structure, and the morphology of the islands, a noticeable temperature dependence of the Se segregation through the Fe islands is found.

  16. Atomic and electronic structure of ultrathin fluoride barrier layers at the oxide/Si interface

    NASA Astrophysics Data System (ADS)

    Pasquali, L.; Montecchi, M.; Nannarone, S.; Boscherini, F.

    2011-09-01

    A SrF2 ultrathin barrier layer on Si(001) is used to form a sharp interface and block reactivity and intermixing between the semiconductor and a Yb2O3 overlayer. Yb2O3/Si(001) and Yb2O3/SrF2/Si(001) interfaces grown in ultra high vacuum by molecular beam epitaxy are studied by photoemission and x-ray absorption fine structure. Without the fluoride interlayer, Yb2O3/Si(001) presents an interface reacted region formed by SiOx and/or silicate compounds, which is about 9 Å thick and increases up to 14-15 Å after annealing at 500-700 °C. A uniform single layer of SrF2 molecules blocks intermixing and reduces the oxidized Si region to 2.4 Å after deposition and to 3.5 Å after annealing at 500 °C. In both cases we estimate a conduction band offset and a valence band offset of ~ 1.7 eV and 2.4 eV between the oxide and Si, respectively. X-ray absorption fine structure measurements at the Yb LIII edge suggest that the Yb oxide films exhibit a significant degree of static disorder with and without the fluoride barrier. Sr K edge measurements indicate that the ultrathin fluoride films are reacted, with the formation of bonds between Si and Sr; the Sr-Sr and Sr-F interatomic distances in the ultrathin fluoride barrier film are relaxed to the bulk value.

  17. Manganese- and iron-dependent marine methane oxidation.

    PubMed

    Beal, Emily J; House, Christopher H; Orphan, Victoria J

    2009-07-10

    Anaerobic methanotrophs help regulate Earth's climate and may have been an important part of the microbial ecosystem on the early Earth. The anaerobic oxidation of methane (AOM) is often thought of as a sulfate-dependent process, despite the fact that other electron acceptors are more energetically favorable. Here, we show that microorganisms from marine methane-seep sediment in the Eel River Basin in California are capable of using manganese (birnessite) and iron (ferrihydrite) to oxidize methane, revealing that marine AOM is coupled, either directly or indirectly, to a larger variety of oxidants than previously thought. Large amounts of manganese and iron are provided to oceans from rivers, indicating that manganese- and iron-dependent AOM have the potential to be globally important.

  18. Superoxide-dependent oxidation of melatonin by myeloperoxidase.

    PubMed

    Ximenes, Valdecir F; Silva, Sueli de O; Rodrigues, Maria R; Catalani, Luiz H; Maghzal, Ghassan J; Kettle, Anthony J; Campa, Ana

    2005-11-18

    Myeloperoxidase uses hydrogen peroxide to oxidize numerous substrates to hypohalous acids or reactive free radicals. Here we show that neutrophils oxidize melatonin to N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK) in a reaction that is catalyzed by myeloperoxidase. Production of AFMK was highly dependent on superoxide but not hydrogen peroxide. It did not require hypochlorous acid, singlet oxygen, or hydroxyl radical. Purified myeloperoxidase and a superoxide-generating system oxidized melatonin to AFMK and a dimer. The dimer would result from coupling of melatonin radicals. Oxidation of melatonin was partially inhibited by catalase or superoxide dismutase. Formation of AFMK was almost completely eliminated by superoxide dismutase but weakly inhibited by catalase. In contrast, production of melatonin dimer was enhanced by superoxide dismutase and blocked by catalase. We propose that myeloperoxidase uses superoxide to oxidize melatonin by two distinct pathways. One pathway involves the classical peroxidation mechanism in which hydrogen peroxide is used to oxidize melatonin to radicals. Superoxide adds to these radicals to form an unstable peroxide that decays to AFMK. In the other pathway, myeloperoxidase uses superoxide to insert dioxygen into melatonin to form AFMK. This novel activity expands the types of oxidative reactions myeloperoxidase can catalyze. It should be relevant to the way neutrophils use superoxide to kill bacteria and how they metabolize xenobiotics.

  19. Investigation of NOx Reduction by Low Temperature Oxidation Using Ozone Produced by Dielectric Barrier Discharge

    NASA Astrophysics Data System (ADS)

    Stamate, Eugen; Irimiea, Cornelia; Salewski, Mirko

    2013-05-01

    NOx reduction by low temperature oxidation using ozone produced by a dielectric barrier discharge generator is investigated for different process parameters in a 6 m long reactor in serpentine arrangement using synthetic dry flue gas with NOx levels below 500 ppm, flows up to 50 slm and temperatures up to 80 °C. The role of different mixing schemes and the impact of a steep temperature gradient are also taken into consideration. The process chemistry is monitored by Fourier transform infrared spectroscopy, chemiluminescence and absorption spectroscopy. The kinetic mechanism during the mixing in a cross flow configuration is investigated using three-dimensional simulations.

  20. Oxidation and degradation of a plasma-sprayed thermal barrier coating system

    SciTech Connect

    Haynes, J.A.; Ferber, M.K.; Porter, W.D.

    1996-04-01

    The isothermal oxidation behavior of thermal barrier coating (TBC) specimens consisting of single-crystal superalloy substrates, vacuum plasma-sprayed Ni-22Cr-10Al-1Y bond coatings and air plasma-sprayed 7.5 wt.% yttria stabilized zirconia top coatings was evaluated by thermogravimetric analysis at 1150{degrees}C for up to 200 hours. Coating durability was assessed by furnace cycling at 1150{degrees}C. Coatings and reaction products were identified by x-ray diffraction, field-emission scanning electron microscopy and energy dispersive spectroscopy.

  1. Morphology-dependent nanocatalysts: rod-shaped oxides.

    PubMed

    Li, Yong; Shen, Wenjie

    2014-03-07

    Nanocatalysts are characterised by the unique nanoscale properties that originate from their highly reduced dimensions. Extensive studies over the past few decades have demonstrated that the size and shape of a catalyst particle on the nanometre scale profoundly affect its reaction performance. In particular, controlling the catalyst particle morphology allows a selective exposure of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms or domains substantially improves catalytic activity, selectivity, and stability. This phenomenon is called morphology-dependent nanocatalysts: catalyst particles with anisotropic morphologies on the nanometre scale greatly affect the reaction performance by selectively exposing the desired facets. In this review, we highlight important progress in morphology-dependent nanocatalysts based on the use of rod-shaped metal oxides with characteristic redox and acid-base features. The correlation between the catalytic properties and the exposed facets verifies the chemical nature of the morphology effect. Moreover, we provide an overview of the interactions between the rod-shaped oxides and the metal nanoparticles in metal-oxide catalyst systems, involving crystal-facet-selective deposition of metal particles onto different crystal facets in the oxide supports. A fundamental understanding of active sites in morphologically tuneable oxides enclosed by the desired reactive facets is expected to direct the development of highly efficient nanocatalysts.

  2. Processing Methods Established To Fabricate Porous Oxide Ceramic Spheres for Thermal Barrier Coating Applications

    NASA Technical Reports Server (NTRS)

    Dynys, Frederick W.

    2003-01-01

    As gas turbine technology advances, the demand for efficient engines and emission reduction requires a further increase in operating temperatures, but combustion temperatures are currently limited by the temperature capability of the engine components. The existing thermal barrier coating (TBC) technology does not provide sufficient thermal load reduction at a 3000 F (1649 C) operating condition. Advancement in thermal barrier coating technology is needed to meet this aggressive goal. One concept for improving thermal barrier coating effectiveness is to design coating systems that incorporate a layer that reflects or scatters photon radiation. This can be achieved by using porous structures. The refractive index mismatch between the solid and pore, the pore size, and the pore density can be engineered to efficiently scatter photon radiation. Under NASA s Ultra-Efficient Engine Technology (UEET) Program, processing methods to fabricate porous ceramic spheres suitable for scattering photon radiation at elevated temperatures have been established. A straightforward templating process was developed at the NASA Glenn Research Center that requires no special processing equipment. The template was used to define particle shape, particle size, and pore size. Spherical organic cation exchange resins were used as a structure-directing template. The cation exchange resins have dual template capabilities that can produce different pore architectures. This process can be used to fabricate both metal oxide and metal carbide spheres.

  3. Ecofriendly Fabrication of Modified Graphene Oxide Latex Nanocomposites with High Oxygen Barrier Performance.

    PubMed

    Guan, Yidan; Meyers, Kevin P; Mendon, Sharathkumar K; Hao, Guangjie; Douglas, Jessica R; Trigwell, Steve; Nazarenko, Sergei I; Patton, Derek L; Rawlins, James W

    2016-12-07

    Large-scale industrial applications of barrier films and coatings that prevent permeation of degradative gases and moisture call for the development of cost-efficient and ecofriendly polymer nanocomposites. Herein, we report the facile fabrication of latex nanocomposites (LNCs) by incorporating surface-modified graphene oxide (mGO) at various loadings (0.025-1.2 wt %) into a styrene-acrylic latex using water as the processing solvent. LNCs fabricated with mGO exhibited significant reductions (up to 67%) in water vapor sorption, resulting in greater environmental stability when compared to LNCs fabricated with equivalent loading of hydrophilic, unmodified GO. The assembly and coalescence of the exfoliated latex/mGO dispersions during the film formation process produced highly dispersed and well-ordered mGO domains with high aspect ratios, where alignment and overlap of the mGO domains improved with increasing mGO content. The addition of only 0.7 vol % (1.2 wt %) mGO led to an 84% decrease (relative to the neat polymer latex film) in oxygen permeability of the LNC films, an excellent barrier performance attributed to the observed LNC film morphologies. This work enables ecofriendly development of mechanically flexible mGO/LNC films with superior barrier properties for many industrial applications including protective coatings, food packaging, and biomedical products.

  4. Hedgehog Signaling Overcomes an EZH2-Dependent Epigenetic Barrier to Promote Cholangiocyte Expansion

    PubMed Central

    Lu, Jie; Almada, Luciana L.; Lomberk, Gwen; Fernandez-Zapico, Martin E.; Urrutia, Raul; Huebert, Robert C.

    2016-01-01

    Background & Aims Developmental morphogens play an important role in coordinating the ductular reaction and portal fibrosis occurring in the setting of cholangiopathies. However, little is known about how membrane signaling events in ductular reactive cells (DRCs) are transduced into nuclear transcriptional changes to drive cholangiocyte maturation and matrix deposition. Therefore, the aim of this study was to investigate potential mechanistic links between cell signaling events and epigenetic regulators in DRCs. Methods Using directed differentiation of induced pluripotent stem cells (iPSC), isolated DRCs, and in vivo models, we examine the mechanisms whereby sonic hedgehog (Shh) overcomes an epigenetic barrier in biliary precursors and promotes both cholangiocyte maturation and deposition of fibronectin (FN). Results We demonstrate, for the first time, that Gli1 influences the differentiation state and fibrogenic capacity of iPSC-derived hepatic progenitors and isolated DRCs. We outline a novel pathway wherein Shh-mediated Gli1 binding in key cholangiocyte gene promoters overcomes an epigenetic barrier conferred by the polycomb protein, enhancer of zeste homolog 2 (EZH2) and initiates the transcriptional program of cholangiocyte maturation. We also define previously unknown functional Gli1 binding sites in the promoters of cytokeratin (CK)7, CK19, and FN. Our in vivo results show that EZH2 KO mice fed the choline-deficient, ethanolamine supplemented (CDE) diet have an exaggerated cholangiocyte expansion associated with more robust ductular reaction and increased peri-portal fibrosis. Conclusion We conclude that Shh/Gli1 signaling plays an integral role in cholangiocyte maturation in vitro by overcoming an EZH2-dependent epigenetic barrier and this mechanism also promotes biliary expansion in vivo. PMID:27936185

  5. The advantages and barriers in the implementation of a substance dependence treatment information system (SDTIS).

    PubMed

    Ajami, Sima; Mellat-Karkevandi, Zahra

    2015-11-01

    Addiction is a phenomenon that causes structural changes in different systems of society. Studies show for planning of addiction prevention and treatment, it is necessary to create an information management system. Substance dependence information systems refer to systems which collect, analyse and report data related to substance dependence information. The aim of this study was to identify advantages and barriers to implement Substance Dependence Treatment Information System (SDTIS). This study was a narrative review. Our review divided into three phases: literature collection, assessing, and selection. We employed the following keywords and their combinations in different areas of articles. In this study, 22 of collected articles and reports were selected based on their relevancy. We found many advantages for a substance dependence treatment information system such as recording sufficient, complete and accurate information and easy and timely access to them and monitoring and enhancing the quality of care received by patients. But we may face some concerns for implementing this information system like taking time and funds from client services, being expensive or even problems regarding the quality of data contained in these information systems. There are some important problems in the way of implementing. In order to overcome these issues, we need to raise community awareness.

  6. Effects of Doping on Thermal Conductivity of Pyrochlore Oxides for Advanced Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Zhu, Dongming; Eslamloo-Grami, Maryam

    2006-01-01

    Pyrochlore oxides of general composition, A2B2O7, where A is a 3(+) cation (La to Lu) and B is a 4(+) cation (Zr, Hf, Ti, etc.) have high melting point, relatively high coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high-temperature thermal barrier coatings. The effect of doping at the A site on the thermal conductivity of a pyrochlore oxide La2Zr2O7, has been investigated. Oxide powders of various compositions La2Zr2O7, La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 were synthesized by the citric acid sol-gel method. These powders were hot pressed into discs and used for thermal conductivity measurements using a steady-state laser heat flux test technique. The rare earth oxide doped pyrochlores La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 had lower thermal conductivity than the un-doped La2Zr2O7. The Gd2O3 and Yb2O3 co-doped composition showed the lowest thermal conductivity.

  7. Role of energy dependent interaction potential in sub-barrier fusion of S2814i +Z9040r system

    NASA Astrophysics Data System (ADS)

    Gautam, Manjeet Singh; Sharma, Manoj K.

    2015-08-01

    We have analyzed the importance of the inelastic surface vibrations of colliding nuclei in the sub-barrier fusion enhancement of S2814i +Z9040r system by using the energy dependent Woods-Saxon potential model (EDWSP model) in conjunction with one dimensional Wong formula and the coupled channel formulation using the code CCFULL. The multi-phonon vibrational states of colliding nuclei seem to impart significant contribution. The coupling between relative motion of reactants and these relevant channels in turn produce anomalously large sub-barrier fusion enhancement over the expectations of one dimensional barrier penetration model. Furthermore, the effects of coupling to inelastic surface excitations are imitated due to energy dependence in the Woods-Saxon potential. In EDWSP model calculations, a wide range of diffuseness parameter much larger than the elastic scattering predictions is needed to account the observed fusion enhancement in the close vicinity of Coulomb barrier.

  8. Thermal Properties of Oxides With Magnetoplumbite Structure for Advanced Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Zhu, Dongming; Eslamloo-Grami, Maryam

    2007-01-01

    Oxides having magnetoplumbite structure are promising candidate materials for applications as high temperature thermal barrier coatings because of their high thermal stability, high thermal expansion, and low thermal conductivity. In this study, powders of LaMgAl11O19, GdMgAl11O19, SmMgAl11O19, and Gd0.7Yb0.3MgAl11O19 magnetoplumbite oxides were synthesized by citric acid sol-gel method and hot pressed into disk specimens. The thermal expansion coefficients (CTE) of these oxide materials were measured from room temperature to 1500 C. The average CTE value was found to be approx.9.6x10(exp -6)/C. Thermal conductivity of these magnetoplumbite-based oxide materials was also evaluated using steady-state laser heat flux test method. The effects of doping on thermal properties were also examined. Thermal conductivity of the doped Gd0.7Yb0.3MgAl11O19 composition was found to be lower than that of the undoped GdMgAl11O19. In contrast, thermal expansion coefficient was found to be independent of the oxide composition and appears to be controlled by the magnetoplumbite crystal structure. Thermal conductivity testing of LaMgAl11O19 and LaMnAl11O19 magnetoplumbite oxide coatings plasma sprayed on NiCrAlY/Rene N5 superalloy substrates indicated resistance of these coatings to sintering even at temperatures as high as 1600 C.

  9. Spin-dependent tunneling time in periodic diluted-magnetic-semiconductor/nonmagnetic-barrier superlattices

    SciTech Connect

    Yang, Ping-Fan; Guo, Yong

    2016-02-01

    We investigate the tunneling time (dwell time) in periodic diluted-magnetic-semiconductor/nonmagnetic-barrier (DMS/NB) superlattices subjected to an external magnetic field. It is found that spin-dependent resonant bands form in the spectra of dwell time, which can be effectively manipulated by not only the external magnetic field but also the geometric parameters of the system. Moreover, an intuitive semiclassical delay is defined to illustrate the behavior of the dwell time, and the former one is shown to be the result of “smoothing out” the latter one. We also find that the dwell time in diluted-magnetic-semiconductor/semiconductor superlattices behaves surprisingly different from the DMS/NB case, especially for spin-down electrons.

  10. In Situ XPS Chemical Analysis of MnSiO3 Copper Diffusion Barrier Layer Formation and Simultaneous Fabrication of Metal Oxide Semiconductor Electrical Test MOS Structures.

    PubMed

    Byrne, Conor; Brennan, Barry; McCoy, Anthony P; Bogan, Justin; Brady, Anita; Hughes, Greg

    2016-02-03

    Copper/SiO2/Si metal-oxide-semiconductor (MOS) devices both with and without a MnSiO3 barrier layer at the Cu/SiO2 interface have been fabricated in an ultrahigh vacuum X-ray photoelectron spectroscopy (XPS) system, which allows interface chemical characterization of the barrier formation process to be directly correlated with electrical testing of barrier layer effectiveness. Capacitance voltage (CV) analysis, before and after tube furnace anneals of the fabricated MOS structures showed that the presence of the MnSiO3 barrier layer significantly improved electric stability of the device structures. Evidence of improved adhesion of the deposited copper layer to the MnSiO3 surface compared to the clean SiO2 surface was apparent both from tape tests and while probing the samples during electrical testing. Secondary ion mass spectroscopy (SIMS) depth profiling measurements of the MOS test structures reveal distinct differences of copper diffusion into the SiO2 dielectric layers following the thermal anneal depending on the presence of the MnSiO3 barrier layer.

  11. Graphene Oxide as an Effective Barrier on a Porous Nanofibrous Membrane for Water Treatment.

    PubMed

    Wang, Jianqiang; Zhang, Pan; Liang, Bin; Liu, Yuxuan; Xu, Tao; Wang, Lifang; Cao, Bing; Pan, Kai

    2016-03-09

    A novel graphene oxide (GO)-based nanofiltration membrane on a highly porous polyacrylonitrile nanofibrous mat (GO@PAN) is prepared for water treatment applications. GO with large lateral size (more than 200 μm) is first synthesized through an improved Hummers method and then assembled on a highly porous nanofibrous mat by vacuum suction method. The prepared GO@PAN membrane is characterized by scanning electron microscopy, transmission electron microscopy, Raman spectrum, X-ray diffraction, and so forth. The results show that graphene oxide can form a barrier on the top of a PAN nanofibrous mat with controllable thickness. The obtained graphene oxide layer exhibits "ideal" pathways (hydrophobic nanochannel) for water molecules between the well-stacked GO nanosheets. Water flux under an extremely low external pressure (1.0 bar) significantly increased due to the unique structure of the GO layer and nanofibrous support. Furthermore, the GO@PAN membrane shows high rejection performance (nearly 100% rejection of Congo red and 56.7% for Na2SO4). A hydrophilic-hydrophobic "gate"-nanochannel model is presented for explaining the water diffusion mechanism through the GO layer. This method for fabrication of the GO membrane on a highly porous support may provide many new opportunities for high performance nanofiltration applications.

  12. Oxidation Resistant Ti-Al-Fe Diffusion Barrier for FeCrAlY Coatings on Titanium Aluminides

    NASA Technical Reports Server (NTRS)

    Brady, Michael P. (Inventor); Smialke, James L. (Inventor); Brindley, William J. (Inventor)

    1996-01-01

    A diffusion barrier to help protect titanium aluminide alloys, including the coated alloys of the TiAl gamma + Ti3Al (alpha2) class, from oxidative attack and interstitial embrittlement at temperatures up to at least 1000 C is disclosed. The coating may comprise FeCrAlX alloys. The diffusion barrier comprises titanium, aluminum, and iron in the following approximate atomic percent: Ti-(50-55)Al-(9-20)Fe. This alloy is also suitable as an oxidative or structural coating for such substrates.

  13. Scale dependent behavior the foredune: Implications for barrier island response to storms and sea level rise

    NASA Astrophysics Data System (ADS)

    Houser, C.; Wernette, P. A.; Weymer, B. A.

    2015-12-01

    The impact of elevated storm surge on a barrier island tends to be considered from a single cross-shore dimension and dependent only on the relative elevations of the storm surge and dune. However, the foredune line is rarely uniform and can exhibit considerable variation in height and width alongshore at a range of length scales ranging from tens of meters to several kilometers. LiDAR data from Santa Rosa Island in northwest Florida, Padre Island, Texas and Assateague Island, Maryland are used to explore how the dune morphology varies alongshore and how this variability is altered by storms and post-storm recovery. While the alongshore variation in dune height can be approximated by a power law, there are scale-dependent variations in the dune that exhibit different responses to storm erosion and post-storm recovery. This suggests that the alongshore variation in dune morphology reflects the history of storm impact and recovery, and that changes in the variance magnitude through time may provide insight into whether the island will be resilient as it transgresses with rising sea level. The difference in variance magnitude at large spatial scales is associated with the framework geology unique to each island and a dominant control on island response to sea level rise.

  14. Exceptional oxygen barrier performance of pullulan nanocomposites with ultra-low loading of graphene oxide

    NASA Astrophysics Data System (ADS)

    Uysal Unalan, Ilke; Wan, Chaoying; Figiel, Łukasz; Olsson, Richard T.; Trabattoni, Silvia; Farris, Stefano

    2015-07-01

    Polymer nanocomposites are increasingly important in food packaging sectors. Biopolymer pullulan is promising in manufacturing packaging films or coatings due to its excellent optical clarity, mechanical strength, and high water-solubility as compared to other biopolymers. This work aims to enhance its oxygen barrier properties and overcome its intrinsic brittleness by utilizing two-dimensional planar graphene oxide (GO) nanoplatelets. It has been found that the addition of only 0.2 wt% of GO enhanced the tensile strength, Young’s modulus, and elongation at break of pullulan films by about 40, 44 and 52%, respectively. The light transmittance at 550 nm of the pullulan/GO films was 92.3% and haze values were within 3.0% threshold, which meets the general requirement for food packaging materials. In particular, the oxygen permeability coefficient of pullulan was reduced from 6337 to 2614 mL μm m-2 (24 h-1) atm-1 with as low as 0.05 wt% of GO loading and further to 1357 mL μm m-2 (24 h-1) atm-1 when GO concentration reached 0.3 wt%. The simultaneous improvement of the mechanical and oxygen barrier properties of pullulan was ascribed to the homogeneous distribution and prevalent unidirectional alignment of GO nanosheets, as determined from the characterization and theoretical modelling results. The exceptional oxygen barrier properties of pullulan/GO nanocomposites with enhanced mechanical flexibility and good optical clarity will add new values to high performance food packaging materials.

  15. Electromechanical Breakdown of Barrier-Type Anodized Aluminum Oxide Thin Films Under High Electric Field Conditions

    NASA Astrophysics Data System (ADS)

    Chen, Jianwen; Yao, Manwen; Yao, Xi

    2016-02-01

    Barrier-type anodized aluminum oxide (AAO) thin films were formed on a polished aluminum substrate via electrochemical anodization in 0.1 mol/L aqueous solution of ammonium pentaborate. Electromechanical breakdown occurred under high electric field conditions as a result of the accumulation of mechanical stress in the film-substrate system by subjecting it to rapid thermal treatment. Before the breakdown event, the electricity of the films was transported in a highly nonlinear way. Immediately after the breakdown event, dramatic cracking of the films occurred, and the cracks expanded quickly to form a mesh-like dendrite network. The breakdown strength was significantly reduced because of the electromechanical coupling effect, and was only 34% of the self-healing breakdown strength of the AAO film.

  16. Schottky barrier at graphene/metal oxide interfaces: insight from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Cheng, Kai; Han, Nannan; Su, Yan; Zhang, Junfeng; Zhao, Jijun

    2017-02-01

    Anode materials play an important role in determining the performance of lithium ion batteries. In experiment, graphene (GR)/metal oxide (MO) composites possess excellent electrochemical properties and are promising anode materials. Here we perform density functional theory calculations to explore the interfacial interaction between GR and MO. Our result reveals generally weak physical interactions between GR and several MOs (including Cu2O, NiO). The Schottky barrier height (SBH) in these metal/semiconductor heterostructures are computed using the macroscopically averaged electrostatic potential method, and the role of interfacial dipole is discussed. The calculated SBHs below 1 eV suggest low contact resistance; thus these GR/MO composites are favorable anode materials for better lithium ion batteries.

  17. Advanced Oxide Material Systems for 1650 C Thermal/Environmental Barrier Coating Applications

    NASA Technical Reports Server (NTRS)

    Zhu, Dong-Ming; Fox, Dennis S.; Bansal, Narottam P.; Miller, Robert A.

    2004-01-01

    Advanced thermal and environmental barrier coatings (TEBCs) are being developed for low-emission SiC/SiC ceramic matrix composite (CMC) combustor and vane applications to extend the CMC liner and vane temperature capability to 1650 C (3000 F) in oxidizing and water-vapor-containing combustion environments. The advanced 1650 C TEBC system is required to have a better high-temperature stability, lower thermal conductivity, and more resistance to sintering and thermal stress than current coating systems under engine high-heat-flux and severe thermal cycling conditions. In this report, the thermal conductivity and water vapor stability of selected candidate hafnia-, pyrochlore- and magnetoplumbite-based TEBC materials are evaluated. The effects of dopants on the materials properties are also discussed. The test results have been used to downselect the TEBC materials and help demonstrate the feasibility of advanced 1650 C coatings with long-term thermal cycling durability.

  18. Schottky barrier at graphene/metal oxide interfaces: insight from first-principles calculations

    PubMed Central

    Cheng, Kai; Han, Nannan; Su, Yan; Zhang, Junfeng; Zhao, Jijun

    2017-01-01

    Anode materials play an important role in determining the performance of lithium ion batteries. In experiment, graphene (GR)/metal oxide (MO) composites possess excellent electrochemical properties and are promising anode materials. Here we perform density functional theory calculations to explore the interfacial interaction between GR and MO. Our result reveals generally weak physical interactions between GR and several MOs (including Cu2O, NiO). The Schottky barrier height (SBH) in these metal/semiconductor heterostructures are computed using the macroscopically averaged electrostatic potential method, and the role of interfacial dipole is discussed. The calculated SBHs below 1 eV suggest low contact resistance; thus these GR/MO composites are favorable anode materials for better lithium ion batteries. PMID:28165485

  19. Advanced Oxide Material Systems For 1650 C Thermal/Environmental Barrier Coating Applications

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Fox, Dennis S.; Bansal, Narottam P.; Miller, Robert A.

    2004-01-01

    Advanced thermal/environmental barrier coatings (T/EBCs) are being developed for low emission SiC/SiC ceramic matrix composite (CMC) combustor and vane applications to extend the CMC liner and vane temperature capability to 1650 C (3000 F) in oxidizing and water-vapor containing combustion environments. The 1650 C T/EBC system is required to have better thermal stability, lower thermal conductivity, and improved sintering and thermal stress resistance than current coating systems. In this paper, the thermal conductivity, water vapor stability and cyclic durability of selected candidate zirconia-/hafnia-, pyrochlore- and magnetoplumbite-based T/EBC materials are evaluated. The test results have been used to downselect the T/EBC coating materials, and help demonstrate advanced 1650OC coatings feasibility with long-term cyclic durability.

  20. Approximate Dependence of Diffusion Barriers on Nearest-Neighbor Configurations on fcc(100) Metals, and Some Consequences

    NASA Astrophysics Data System (ADS)

    Einstein, T. L.; Jacobsen, J.; Schiff, C.

    1997-03-01

    To simulate epitaxial growth, one needs an a priori understanding of how atomic diffusion barriers depend on the occupation of near-neighbor sites of the initial and final positions. From a histogram of such barriers computed for Cu/Cu(100) using the embedded atom method (EAM), Karimi et al.(M. Karimi, T. Tomkowski, G. Vidali, and O. Biham, Phys. Rev. B 52), 5364 (1995); O. Biham et al., preprint found that these energies fell into four groups. They proposed a simple approximation for the local-configuration dependence of the energy barriers. From a reexamination of these energies, using effective medium theory, we propose an approximation which also depends solely on near-neighbor occupations but accounts better for the energy barriers. The scheme is comparably accurate for Ag/Ag(100), but requires some modification for Ni/Ni(100). We also describe some noteworthy effects of fcc geometry in this approximation, particularly a mechanism which, like the Ehrlich-Schwoebel barrier, enhances roughness with increasing temperature. In the next talk we describe and compare simulations using both approximations.

  1. Solvent-dependent on/off valving using selectively permeable barriers in paper microfluidics.

    PubMed

    Salentijn, G Ij; Hamidon, N N; Verpoorte, E

    2016-03-21

    We report on a new way to control solvent flows in paper microfluidic devices, based on the local patterning of paper with alkyl ketene dimer (AKD) to form barriers with selective permeability for different solvents. Production of the devices is a two-step process. In the first step, AKD-treated paper (hydrophobic) is exposed to oxygen plasma for re-hydrophilization. 3D-printed masks are employed to shield certain areas of this paper to preserve well-defined hydrophobic patterns. In the second step, concentrated AKD in hexane is selectively deposited onto already hydrophobic regions of the paper to locally increase the degree of hydrophobicity. Hydrophilic areas formed in the previous oxygen plasma step are protected from AKD by wetting them with water first to prevent the AKD hexane solution from entering them (hydrophilic exclusion). Characterization of the patterns after both steps shows that reproducible patterns are obtained with linear dependence on the dimensions of the 3D-printed masks. This two-step methodology leads to differential hydrophobicity on the paper: (i) hydrophilic regions, (ii) low-load AKD gates, and (iii) high-load AKD walls. The gates are impermeable to water, yet can be penetrated by most alcohol/water mixtures; the walls cannot. This concept for solvent-dependent on/off valving is demonstrated in two applications. In the first example, a device was developed for multi-step chemical reactions. Different compounds can be spotted separately (closed gates). Upon elution with an alcohol/water mixture, the gates become permeable and the contents are combined. In the second example, volume-defined sampling is introduced. Aqueous sample is allowed to wick into a device and fill a sample chamber. The contents of this sample chamber are eluted perpendicularly with an alcohol/water mixture through a selectively permeable gate. This system was tested with dye solution, and a linear dependence of magnitude of the signal on the sample chamber size was

  2. Nitric oxide attenuates hydrogen peroxide-induced barrier disruption and protein tyrosine phosphorylation in monolayers of intestinal epithelial cell.

    PubMed

    Katsube, Takanori; Tsuji, Hideo; Onoda, Makoto

    2007-06-01

    The intestinal epithelium provides a barrier to the transport of harmful luminal molecules into the systemic circulation. A dysfunctional epithelial barrier is closely associated with the pathogenesis of a variety of intestinal and systemic disorders. We investigated here the effects of nitric oxide (NO) and hydrogen peroxide (H(2)O(2)) on the barrier function of a human intestinal epithelial cell line, Caco-2. When treated with H(2)O(2), Caco-2 cell monolayers grown on permeable supports exhibited several remarkable features of barrier dysfunction as follows: a decrease in transepithelial electrical resistance, an increase in paracellular permeability to dextran, and a disruption of the intercellular junctional localization of the scaffolding protein ZO-1. In addition, an induction of tyrosine phosphorylation of numerous cellular proteins including ZO-1, E-cadherin, and beta-catenin, components of tight and adherens junctions, was observed. On the other hand, combined treatment of Caco-2 monolayers with H(2)O(2) and an NO donor (NOC5 or NOC12) relieved the damage to the barrier function and suppressed the protein tyrosine phosphorylation induced by H(2)O(2) alone. These results suggest that NO protects the barrier function of intestinal epithelia from oxidative stress by modulating some intracellular signaling pathways of protein tyrosine phosphorylation in epithelial cells.

  3. The oxidative burst reaction in mammalian cells depends on gravity.

    PubMed

    Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

    2013-12-20

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

  4. The oxidative burst reaction in mammalian cells depends on gravity

    PubMed Central

    2013-01-01

    Gravity has been a constant force throughout the Earth’s evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in “functional weightlessness” were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and

  5. Low-index nanopatterned barrier for hybrid oxide-free III-V silicon conductive bonding.

    PubMed

    Bougot-Robin, Kristelle; Talneau, Anne; Benisty, Henri

    2014-09-22

    Oxide-free bonding of a III-V active stack emitting at 1300-1600 nm to a silicon-on-insulator wafer offers the capability to electrically inject lasers from the silicon side. However, a typical 500-nm-thick silicon layer notably attracts the fundamental guided mode of the silicon + III-V stack, a detrimental feature compared to established III-V Separate-Confinement Heterostructure (SCH) stacks. We experimentally probe with photoluminescence as an internal light source the guiding behavior for oxide-free bonding to a nanopatterned silicon wafer that acts as a low-index barrier. We use a sub-wavelength square array of small holes as an effective "low-index silicon" medium. It is weakly modulated along one dimension (superperiodic array) to outcouple the resulting guided modes to free space, where we use an angle-resolved spectroscopy study. Analysis of experimental branches confirms the capability to operate with a fundamental mode well localized in the III-V heterostructures.

  6. Temperature-dependent Schottky barrier in high-performance organic solar cells

    PubMed Central

    Li, Hui; He, Dan; Zhou, Qing; Mao, Peng; Cao, Jiamin; Ding, Liming; Wang, Jizheng

    2017-01-01

    Organic solar cells (OSCs) have attracted great attention in the past 30 years, and the power conversion efficiency (PCE) now reaches around 10%, largely owning to the rapid material developments. Meanwhile with the progress in the device performance, more and more interests are turning to understanding the fundamental physics inside the OSCs. In the conventional bulk-heterojunction architecture, only recently it is realized that the blend/cathode Schottky junction serves as the fundamental diode for the photovoltaic function. However, few researches have focused on such junctions, and their physical properties are far from being well-understood. In this paper based on PThBDTP:PC71BM blend, we fabricated OSCs with PCE exceeding 10%, and investigated temperature-dependent behaviors of the junction diodes by various characterization including current-voltage, capacitance-voltage and impedance measurements between 70 to 290 K. We found the Schottky barrier height exhibits large inhomogeneity, which can be described by two sets of Gaussian distributions. PMID:28071700

  7. Temperature-dependent Schottky barrier in high-performance organic solar cells.

    PubMed

    Li, Hui; He, Dan; Zhou, Qing; Mao, Peng; Cao, Jiamin; Ding, Liming; Wang, Jizheng

    2017-01-10

    Organic solar cells (OSCs) have attracted great attention in the past 30 years, and the power conversion efficiency (PCE) now reaches around 10%, largely owning to the rapid material developments. Meanwhile with the progress in the device performance, more and more interests are turning to understanding the fundamental physics inside the OSCs. In the conventional bulk-heterojunction architecture, only recently it is realized that the blend/cathode Schottky junction serves as the fundamental diode for the photovoltaic function. However, few researches have focused on such junctions, and their physical properties are far from being well-understood. In this paper based on PThBDTP:PC71BM blend, we fabricated OSCs with PCE exceeding 10%, and investigated temperature-dependent behaviors of the junction diodes by various characterization including current-voltage, capacitance-voltage and impedance measurements between 70 to 290 K. We found the Schottky barrier height exhibits large inhomogeneity, which can be described by two sets of Gaussian distributions.

  8. Temperature-dependent Schottky barrier in high-performance organic solar cells

    NASA Astrophysics Data System (ADS)

    Li, Hui; He, Dan; Zhou, Qing; Mao, Peng; Cao, Jiamin; Ding, Liming; Wang, Jizheng

    2017-01-01

    Organic solar cells (OSCs) have attracted great attention in the past 30 years, and the power conversion efficiency (PCE) now reaches around 10%, largely owning to the rapid material developments. Meanwhile with the progress in the device performance, more and more interests are turning to understanding the fundamental physics inside the OSCs. In the conventional bulk-heterojunction architecture, only recently it is realized that the blend/cathode Schottky junction serves as the fundamental diode for the photovoltaic function. However, few researches have focused on such junctions, and their physical properties are far from being well-understood. In this paper based on PThBDTP:PC71BM blend, we fabricated OSCs with PCE exceeding 10%, and investigated temperature-dependent behaviors of the junction diodes by various characterization including current-voltage, capacitance-voltage and impedance measurements between 70 to 290 K. We found the Schottky barrier height exhibits large inhomogeneity, which can be described by two sets of Gaussian distributions.

  9. Influence of the microstructure and topography on the barrier properties of oxide scales generated on blasted Ti6Al4V surfaces.

    PubMed

    Barranco, V; Escudero, M L; García-Alonso, M C

    2011-06-01

    The long-term interfacial bond between an implant and bone may be improved by creating a rough surface on the implant in order to increase the surface area available for bone/implant apposition. A natural consequence of surface roughening is an increase in metal ion release, which is itself a surface dominated process. Based on this fact, the aim of this work is to study the influence of the microstructure and topography on the barrier properties of oxide scales thermally generated at 700 °C for 1h on Ti6Al4V surfaces after blasting with Al(2)O(3) particles (coarse) or SiO(2) and ZrO(2) particles (fine). The microstructural and topographical characterization of the thermally treated blasted surfaces has been studied by means of scanning electron microscopy coupled with energy dispersive X-ray analysis, contact profilometry and X-ray diffraction. The barrier properties and corrosion behaviour of the oxide layers have been studied by means of electrochemical impedance spectroscopy (EIS) in Hank's solution. Thermal treatment at 700 °C for 1h promotes the formation of oxide scales with different morphologies and crystalline structures depending on the degree of deformation of the blasted surface. The oxide scale grown on the finely blasted sample has a pine needle-like morphology which is mainly formed of anatase TiO(2). In contrast, the oxide scale grown on the coarsely blasted sample has a globular morphology formed mainly of rutile TiO(2). The differences in morphology, i.e. fine or coarse, of the oxide scales influence the corrosion response of the blasted thermally treated samples in Hank's solution. The EIS results permit evaluation of the different oxide scales from the capacitance and resistance values obtained in the high-frequency region and show a good correlation between the morphology and barrier properties. Oxidation treatment at 700 °C for 1h of Ti6Al4V samples coarsely blasted with Al(2)O(3) improves the corrosion behaviour due to an increase in the

  10. Temperature dependent electrical transport of disordered reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Muchharla, Baleeswaraiah; Narayanan, T. N.; Balakrishnan, Kaushik; Ajayan, Pulickel M.; Talapatra, Saikat

    2014-06-01

    We report on the simple route for the synthesis of chemically reduced graphene oxide (rGO) using ascorbic acid (a green chemical) as a reducing agent. Temperature-dependent electrical transport properties of rGO thin films have been studied in a wide range (50 K T 400 K) of temperature. Electrical conduction in rGO thin films was displayed in two different temperature regimes. At higher temperatures, Arrhenius-like temperature dependence of resistance was observed indicating a band gap dominating transport behavior. At lower temperatures, the rGO sample showed a conduction mechanism consistent with Mott's two-dimensional variable range hopping (2D-VRH). An unsaturated negative magnetoresistance (MR) was observed up to 3 T field. A decrease in negative MR at high temperatures is attributed to the phonon scattering of charge carriers.

  11. Time-dependent behavior and thermal fracture in functionally graded thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Rangaraj, Sudarshan V.

    The objective of this research was to characterize the thermo-mechanical response and fracture behavior of zirconia-bond coat (BC) alloy functionally graded thermal barrier coatings (TBCs) under high heat flux thermal loads. Under the resulting high surface temperatures and gradients, the coatings develop surface cracks as well as TBC-BC interface cracks. Time-dependent (viscoplastic) deformations in the TBC layers were the major cause for surface and interface fracture. Micromechanics models were developed to estimate the effective thermo-elastic properties and time-dependent response of YSZ-BC alloy particulate composites that constitute the layers of a graded TBC. These effective properties were then utilized in numerical fracture mechanics analyses to study the influence of coating architecture on its fracture response. The driving force for surface crack initiation and for the formation of multiple surface cracks was found to increase with compositional gradation. It was also found that replacing a single-layer (non-graded) TBC by a functionally graded TBC of comparable thermal resistance resulted in a reduced driving force for interface crack growth. The formation of multiple surface cracks and its higher flexural stiffness were found to impart a graded TBC with a higher resistance to interface fracture. Methodologies were developed to estimate the fracture resistance and toughness of graded TBCs. It was found that both the single-layer zirconia TBC as well as functionally graded TBCs showed an increase in fracture resistance with crack advance. The addition of BC alloy was found to enhance the fracture toughness of the layers in a graded TBC. However, the magnitude of toughness enhancement seen was not very significant. Laser thermal shock experiments were conducted on plasma sprayed single-layer zirconia-BC alloy composite coatings. Coatings with three different compositions, of similar thermal resistance were considered. It was found that coatings with a

  12. Investigation on edge fringing effect and oxide thickness dependence of inversion current in metal-oxide-semiconductor tunneling diodes with comb-shaped electrodes

    NASA Astrophysics Data System (ADS)

    Lin, Chien-Chih; Hsu, Pei-Lun; Lin, Li; Hwu, Jenn-Gwo

    2014-03-01

    A particular edge-dependent inversion current behavior of metal-oxide-semiconductor (MOS) tunneling diodes was investigated utilizing square and comb-shaped electrodes. The inversion tunneling current exhibits the strong dependence on the tooth size of comb-shaped electrodes and oxide thickness. Detailed illustrations of current conduction mechanism are developed by simulation and experimental measurement results. It is found that the electron diffusion current and Schottky barrier height lowering for hole tunneling current both contribute on inversion current conduction. In MOS tunneling photodiode applications, the photoresponse can be improved by decreasing SiO2 thickness and using comb-shaped electrodes with smaller tooth spacing. Meantime, the high and steady photosensitivity can also be approached by introducing HfO2 into dielectric stacks.

  13. Excitation wavelength dependent fluorescence of graphene oxide controlled by strain.

    PubMed

    Cushing, Scott K; Ding, Weiqiang; Chen, Gang; Wang, Chao; Yang, Feng; Huang, Fuqiang; Wu, Nianqiang

    2017-02-09

    Unlike conventional fluorophores, the fluorescence emission of graphene oxide (GO) sheets can shift hundreds of nanometers as the excitation wavelength increases. The excitation wavelength dependent fluorescence is referred to as a giant red-edge effect and originates in a local reorganization potential slowing down the solvation dynamics of the excited state to the same time scale as the fluorescence lifetime. The present work has discovered that out-of-plane strain in the graphene oxide sheet leads to the intra-layer interaction necessary to slow down the solvation time scale. The oxygen percentage, dopant percentage, disorder, and strain are correlated with the presence and extent of the red-edge effect in oxygen, boron, nitrogen, and fluorine doped graphene oxide. Of these commonly cited possibilities, only out-of-plane strain is directly correlated to the red-edge effect. Furthermore, it is shown that the extent of the red-edge effect, or how far the emission wavelength can shift with increasing excitation wavelength, can be tuned by the electronegativity of the dopant. The present work interprets why the giant red-edge effect is present in some GO sheets but not in other GO sheets.

  14. Size-dependent magnetic properties of branchlike nickel oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Liu, Dan; Li, Dongsheng; Yang, Deren

    2017-01-01

    Branchlike nickel oxide nanocrystals with narrow size distribution are obtained by a solution growth method. The size-dependent of magnetic properties of the nickel oxides were investigated. The results of magnetic characterization indicate that the NiO nanocrystals with size below 12.8 nm show very weak ferromagnetic state at room temperature due to the uncompensated spins. Both of the average blocking temperature (Tb) and the irreversible temperature (Tirr) increase with the increase of nanoparticle sizes, while both the remnant magnetization and the coercivity at 300 K increase with the decrease of the particle sizes. Moreover, the disappearance of two-magnon (2M) band and redshift of one-phonon longitudinal (1LO) and two-phonon LO in vibrational properties due to size reduction are observed. Compared to the one with the spherical morphological, it is also found that nano-structured nickel oxides with the branchlike morphology have larger remnant magnetization and the coercivity at 5 K due to their larger surface-to-volume ratio and greater degree of broken symmetry at the surface or the higher proportion of broken bonds.

  15. Reduced temperature and bias-voltage dependence of the magnetoresistance in magnetic tunnel junctions with Hf-inserted Al2O3 barrier

    NASA Astrophysics Data System (ADS)

    Park, Byong Guk; Lee, Taek Dong

    2002-09-01

    A modified tunnel barrier structure for the magnetic tunnel junction (MTJ) was fabricated by inserting a Hf layer in the middle of the Al2O3 tunnel barrier. MTJs with the Hf-inserted barrier show a higher tunnel mangnetoresistance (TMR) ratio and weaker temperature and bias-voltage dependence of TMR compared to the MTJs with a conventional Al2O3 barrier. The enhancement of the TMR ratio and the reduction of the temperature and bias-voltage dependence were attributed to the reduction of defects in the barrier.

  16. Carbonylation and disassembly of the F-actin cytoskeleton in oxidant induced barrier dysfunction and its prevention by epidermal growth factor and transforming growth factor α in a human colonic cell line

    PubMed Central

    Banan, A; Zhang, Y; Losurdo, J; Keshavarzian, A

    2000-01-01

    BACKGROUND—Intestinal barrier dysfunction concomitant with high levels of reactive oxygen metabolites (ROM) in the inflamed mucosa have been observed in inflammatory bowel disease (IBD). The cytoskeletal network has been suggested to be involved in the regulation of barrier function. Growth factors (epidermal growth factor (EGF) and transforming growth factor α (TGF-α)) protect gastrointestinal barrier integrity against a variety of noxious agents. However, the underlying mechanisms of oxidant induced disruption and growth factor mediated protection remain elusive.
AIMS—To determine: (1) if oxidation and disassembly of actin (a key cytoskeletal component) plays a major role in ROM induced epithelial monolayer barrier dysfunction; and (2) if growth factor mediated protection involves prevention of theses alterations.
METHODS—Caco-2 monolayers were preincubated with EGF, TGF-α, or vehicle before incubation with ROM (H2O2 or HOCl). Effects on cell integrity, barrier function, and G- and F-actin (oxidation, disassembly, and assembly) were determined.
RESULTS—ROM dose dependently and significantly increased F- and G-actin oxidation (carbonylation), decreased the stable F-actin fraction (index of stability), and increased the monomeric G-actin fraction (index of disassembly). Concomitant with these changes were disruption of the actin cytoskeleton and loss of the monolayer barrier function. In contrast, growth factor pretreatment decreased actin oxidation and enhanced the stable F-actin, while in concert prevented actin disruption and restored normal barrier function of monolayers exposed to ROM. Cytochalasin-D, an inhibitor of actin assembly, not only caused actin disassembly and barrier dysfunction but also abolished the protective action of growth factors. Moreover, an actin stabilising agent, phalloidin, mimicked the protective actions of the growth factors.
CONCLUSIONS—Oxidation, disassembly, and instability of the actin cytoskeleton appears to

  17. Chromium oxide as a metal diffusion barrier layer: An x-ray absorption fine structure spectroscopy study

    NASA Astrophysics Data System (ADS)

    Ahamad Mohiddon, Md.; Lakshun Naidu, K.; Ghanashyam Krishna, M.; Dalba, G.; Ahmed, S. I.; Rocca, F.

    2014-01-01

    The interaction at the interface between chromium and amorphous Silicon (a-Si) films in the presence of a sandwich layer of chromium oxide is investigated using X-ray absorption fine structure (XAFS) spectroscopy. The oxidized interface was created, in situ, prior to the deposition of a 400 nm tick a-Si layer over a 50 nm tick Cr layer. The entire stack of substrate/metallic Cr/Cr2O3/a-Si was then annealed at temperatures from 300 up to 700 °C. Analysis of the near edge and extended regions of each XAFS spectrum shows that only a small fraction of Cr is able to diffuse through the oxide layer up to 500 °C, while the remaining fraction is buried under the oxide layer in the form of metallic Cr. At higher temperatures, diffusion through the oxide layer is enhanced and the diffused metallic Cr reacts with a-Si to form CrSi2. At 700 °C, the film contains Cr2O3 and CrSi2 without evidence of unreacted metallic Cr. The activation energy and diffusion coefficient of Cr are quantitatively determined in the two temperature regions, one where the oxide acts as diffusion barrier and another where it is transparent to Cr diffusion. It is thus demonstrated that chromium oxide can be used as a diffusion barrier to prevent metal diffusion into a-Si.

  18. Barriers to community-based drug dependence treatment: implications for police roles, collaborations and performance indicators

    PubMed Central

    Ma, Yi; Du, Chunhua; Cai, Thomas; Han, Qingfeng; Yuan, Huanhuan; Luo, Tingyan; Ren, Guoliang; Mburu, Gitau; Wang, Bangyuan; Golichenko, Olga; Zhang, Chaoxiong

    2016-01-01

    Introduction Worldwide, people who use drugs (PWUD) are among the populations at highest risk for HIV infection. In China, PWUD are primarily sentenced to compulsory detainment centres, in which access to healthcare, including HIV treatment and prevention services, is limited or non-existent. In 2008, China's 2008 Anti-Drug Law encouraged the development and use of community-based drug dependence rehabilitation, yet there is limited evidence evaluating the efficacy and challenges of this model in China. In this study, we explore these challenges and describe how cooperation between law enforcement and health departments can meet the needs of PWUD. Methods In 2015, we conducted semi-structured, in-depth interviews with all four staff members and 16 clients of the Ping An Centre No. 1 for community-based drug treatment, three local police officers and three officials from the local Centre for Disease Control. Interviews explored obstacles in implementing community-based drug dependence treatment and efforts to resolve these difficulties. Transcripts were coded and analyzed with qualitative data analysis software (MAXQDA 11). Results We identified three challenges to community-based drug treatment at the Ping An Centre No. 1: (1) suboptimal coordination among parties involved, (2) a divergence in attitudes towards PWUD and harm reduction between law enforcement and health officials and (3) conflicting performance targets for police and health officials that undermine the shared goal of treatment. We also identified the take-home methadone maintenance treatment model at the Ping An Centre No. 1 as an example of an early successful collaboration between the police, the health department and PWUD. Conclusions To overcome barriers to effective community-based drug treatment, we recommend aligning the goals of law enforcement and public health agencies towards health-based performance indicators. Furthermore, tensions between PWUD and police need to be addressed and trust

  19. Sputter Deposition of Yttrium-Barium Superconductor and Strontium Titanium Oxide Barrier Layer Thin Films

    NASA Astrophysics Data System (ADS)

    Truman, James Kelly

    1992-01-01

    The commercial application of superconducting rm YBa_2Cu_3O_{7 -x} thin films requires the development of deposition methods which can be used to reproducibly deposit films with good superconducting properties on insulating and semiconducting substrates. Sputter deposition is the most popular method to fabricate Y-Ba-Cu-O superconductor thin films, but when used in the standard configuration suffers from a deviation between the compositions of the Y-Ba-Cu-O sputter target and deposited films, which is thought to be primarily due to resputtering of the film by negative ions sputtered from the target. In this study, the negative ions were explicitly identified and were found to consist predominantly O^-. The sputter yield of O^- was found to depend on the Ba compound used in the fabrication of Y -Ba-Cu-O targets and was related to the electronegativity difference between the components. An unreacted mixture of rm Y_2O_3, CuO, and BaF_2 was found to have the lowest O^- yield among targets with Y:Ba:Cu = 1:2:3. The high yield of O^- from rm YBa_2Cu_3O _{7-x} was found to depend on the target temperature and be due to the excess oxygen present. The SIMS negative ion data supported the composition data for sputter-deposited Y-Ba-Cu-O films. Targets using BaF _2 were found to improve the Ba deficiency, the run-to-run irreproducibility and the nonuniformity of the film composition typically found in sputtered Y -Ba-Cu-O films. Superconducting Y-Ba-Cu-O films were formed on SrTiO_3 substrates by post-deposition heat treatment of Y-Ba-Cu-O-F films in humid oxygen. The growth of superconducting rm YBa_2Cu_3O_{7-x}, thin films on common substrates such as sapphire or silicon requires the use of a barrier layer to prevent the deleterious interaction which occurs between Y-Ba-Cu-O films and these substrates. Barrier layers of SrTiO_3 were studied and found to exhibit textured growth with a preferred (111) orientation on (100) Si substrates. However, SrTiO_3 was found to be

  20. Exhaled nitric oxide is age-dependent in asthma.

    PubMed

    Avital, Avraham; Uwyyed, Kamal; Berkman, Neville; Bar-Yishay, Ephraim; Godfrey, Simon; Springer, Chaim

    2003-11-01

    We determined whether the exhaled nitric oxide (eNO) level in asthmatics is age-dependent. Eighty-seven asthmatic patients aged 2-41 years were studied. Hyperreactivity to adenosine 5'-monophosphate (AMP) was used to confirm asthma (dependent, with lower values in young children.

  1. Microbubble type and distribution dependence of focused ultrasound-induced blood-brain barrier opening.

    PubMed

    Wang, Shutao; Samiotaki, Gesthimani; Olumolade, Oluyemi; Feshitan, Jameel A; Konofagou, Elisa E

    2014-01-01

    Focused ultrasound, in the presence of microbubbles, has been used non-invasively to induce reversible blood-brain barrier (BBB) opening in both rodents and non-human primates. This study was aimed at identifying the dependence of BBB opening properties on polydisperse microbubble (all clinically approved microbubbles are polydisperse) type and distribution by using a clinically approved ultrasound contrast agent (Definity microbubbles) and in-house prepared polydisperse (IHP) microbubbles in mice. A total of 18 C57 BL/6 mice (n = 3) were used in this study, and each mouse was injected with either Definity or IHP microbubbles via the tail vein. The concentration and size distribution of activated Definity and IHP microbubbles were measured, and the microbubbles were diluted to 6 × 10(8)/mL before injection. Immediately after microbubble administration, mice were subjected to focused ultrasound with the following parameters: frequency = 1.5 MHz, pulse repetition frequency = 10 Hz, 1000 cycles, in situ peak rarefactional acoustic pressures = 0.3, 0.45 and 0.6 MPa for a sonication duration of 60 s. Contrast-enhanced magnetic resonance imaging was used to confirm BBB opening and allowed for image-based analysis. Permeability of the treated region and volume of BBB opening did not significantly differ between the two types of microbubbles (p > 0.05) at peak rarefractional acoustic pressures of 0.45 and 0.6 MPa, whereas IHP microbubbles had significantly higher permeability and opening volume (p < 0.05) at the relatively lower pressure of 0.3 MPa. The results from this study indicate that microbubble type and distribution could have significant effects on focused ultrasound-induced BBB opening at lower pressures, but less important effects at higher pressures, possibly because of the stable cavitation that governs the former. This difference may have become less significant at higher pressures, where inertial cavitation typically occurs.

  2. Suppression of spin transport in ferromagnet/oxide/semiconductor junctions by magnetic impurities in the tunnel barrier

    NASA Astrophysics Data System (ADS)

    Spiesser, Aurélie; Saito, Hidekazu; Yuasa, Shinji; Jansen, Ron

    2016-10-01

    We have studied how the insertion of sub-monolayer amounts of Mn impurities in the middle of the oxide tunnel barrier of Fe/GeO2 on p-type Ge affects the spin transport, using three-terminal Hanle measurements. Strikingly, the magnitude of the Hanle spin voltage is strongly reduced by increasing the amount of Mn dopants and is even completely absent for devices having an amount of Mn impurities equivalent to a 0.2-nm-thick layer. This demonstrates that magnetic impurities in the tunnel barrier are detrimental to the spin transport in ferromagnet/oxide/semiconductor junctions, and that the localized states associated with such magnetic impurities do not produce three-terminal Hanle spin signals.

  3. Anaerobic, Nitrate-Dependent Oxidation of U(IV) Oxide Minerals by the Chemolithoautotrophic Bacterium Thiobacillus denitrificans

    PubMed Central

    Beller, Harry R.

    2005-01-01

    Under anaerobic conditions and at circumneutral pH, cells of the widely distributed, obligate chemolithoautotrophic bacterium Thiobacillus denitrificans oxidatively dissolved synthetic and biogenic U(IV) oxides (uraninite) in nitrate-dependent fashion: U(IV) oxidation required the presence of nitrate and was strongly correlated with nitrate consumption. This is the first report of anaerobic U(IV) oxidation by an autotrophic bacterium. PMID:15812053

  4. Anaerobic, Nitrate-Dependent Oxidation of U(IV) Oxide Minerals by the Chemolithoautotrophic Bacterium Thiobacillus denitrificans

    SciTech Connect

    Beller, H R

    2004-06-25

    Under anaerobic conditions and at circumneutral pH, cells of the widely-distributed, obligate chemolithoautotrophic bacterium Thiobacillus denitrificans oxidatively dissolved synthetic and biogenic U(IV) oxides (uraninite) in nitrate-dependent fashion: U(IV) oxidation required the presence of nitrate and was strongly correlated to nitrate consumption. This is the first report of anaerobic U(IV) oxidation by an autotrophic bacterium.

  5. pH dependent protein stability: A quantitative approach based on Kramer's barrier escape

    NASA Astrophysics Data System (ADS)

    Chatterjee, Debarati

    2015-01-01

    The folding-unfolding mechanism of a protein in a living cell is the result of its molecular response to various perturbations due to changes in the chemical environment such as pH, ion concentration, ligand binding and many other complex chemical reactions. In this letter, a theoretical scheme based on single molecule force spectroscopy experiments and related theories, has been followed to capture the effect of the change of pH for a slow protonation-coupled folding-unfolding process, and the free energy landscape has been quantified in terms of protonation numbers, barrier height and pH, following Kramer's barrier crossing formalism.

  6. Gold-thickness-dependent Schottky barrier height for charge transfer in metal-assisted chemical etching of silicon.

    PubMed

    Zuo, Zewen; Cui, Guanglei; Shi, Yi; Liu, Yousong; Ji, Guangbin

    2013-04-26

    Large-area, vertically aligned silicon nanowires with a uniform diameter along the height direction were fabricated by combining in situ-formed anodic aluminum oxide template and metal-assisted chemical etching. The etching rate of the Si catalyzed using a thick Au mesh is much faster than that catalyzed using a thin one, which is suggested to be induced by the charge transport process. The thick Au mesh in contact with the Si produces a low Au/Si Schottky barrier height, facilitating the injection of electronic holes from the Au to the Si, thus resulting in a high etching rate.

  7. The Development of HfO2-Rare Earth Based Oxide Materials and Barrier Coatings for Thermal Protection Systems

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Harder, Bryan James

    2014-01-01

    Advanced hafnia-rare earth oxides, rare earth aluminates and silicates have been developed for thermal environmental barrier systems for aerospace propulsion engine and thermal protection applications. The high temperature stability, low thermal conductivity, excellent oxidation resistance and mechanical properties of these oxide material systems make them attractive and potentially viable for thermal protection systems. This paper will focus on the development of the high performance and high temperature capable ZrO2HfO2-rare earth based alloy and compound oxide materials, processed as protective coating systems using state-or-the-art processing techniques. The emphasis has been in particular placed on assessing their temperature capability, stability and suitability for advanced space vehicle entry thermal protection systems. Fundamental thermophysical and thermomechanical properties of the material systems have been investigated at high temperatures. Laser high-heat-flux testing has also been developed to validate the material systems, and demonstrating durability under space entry high heat flux conditions.

  8. Size-dependent selectivity and activity of silver nanoclusters in the partial oxidation of propylene to propylene oxide and acrolein : A joint experimental and theoretical study.

    SciTech Connect

    Molina, L M.; Lee, S.; Sell, K.; Barcaro, G.; Fortunelli, A.; Lee, B.; Seifert, S.; Winans, R. E.; Elam, J. W.; Pellin, M. J.; Barke, I.; von Oeynhausen, V.; Lei, Y.; Meyer, R. J.; Alonso, J. A.; Fraile-Rodriguez, A.; Kleibert, A.; Giorgio, S.; Henry, C. R.; Heinz Meiwes-Broer, K.; Vadja, S.; Univ. de Valladolid; Univ. Rostock; IPCF-CNR; Univ. of Illinois at Chicago; Swiss Light Source; CINaM-CNRS and Aix-Marseille Univ.; Yale Univ.

    2011-02-02

    Model silver nanocatalysts between 9 and 23 nm in size were prepared by size-selected cluster deposition from a free cluster beam on amorphous alumina films and their size-dependent catalytic performance studied in the partial oxidation of propylene under realistic reaction conditions. Smaller clusters preferentially produced acrolein, while the 23 nm particles were considerably more selective towards the formation of propylene oxide, at reaction rates far exceeding those previously reported for larger silver particles. The activity of clusters dropped significantly with increasing particle size. First-principle calculations, of the activation energies for oxygen adsorption and its dissociation, at variable surface coverage yielded surface energies which resulted in particle shapes resembling the experimentally observed shapes of partially oxidized silver clusters. The calculated activation barriers for propylene oxide and acrolein formation on various facets and on the edges of the nanoparticles provided detailed information about the energetics of the competing reaction pathways. The size- and corresponding morphology dependent theoretical activity and selectivity are in good accord with experimental observations.

  9. Temperature dependence of graphene oxide reduced by hydrazine hydrate.

    PubMed

    Ren, Peng-Gang; Yan, Ding-Xiang; Ji, Xu; Chen, Tao; Li, Zhong-Ming

    2011-02-04

    Graphene oxide (GO) was successfully prepared by a modified Hummer's method. The reduction effect and mechanism of the as-prepared GO reduced with hydrazine hydrate at different temperatures and time were characterized by x-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), x-ray diffractions (XRD), Raman spectroscopy and thermo-gravimetric analysis (TGA). The results showed that the reduction effect of GO mainly depended on treatment temperature instead of treatment time. Desirable reduction of GO can only be obtained at high treatment temperature. Reduced at 95 °C for 3 h, the C/O atomic ratio of GO increased from 3.1 to 15.1, which was impossible to obtain at low temperatures, such as 80, 60 or 15 °C, even for longer reduction time. XPS, 13C NMR and FTIR results show that most of the epoxide groups bonded to graphite during the oxidation were removed from GO and form the sp(2) structure after being reduced by hydrazine hydrate at high temperature (>60 °C), leading to the electric conductivity of GO increasing from 1.5 × 10(-6) to 5 S cm(-1), while the hydroxyls on the surface of GO were not removed by hydrazine hydrate even at high temperature. Additionally, the FTIR, XRD and Raman spectrum indicate that the GO reduced by hydrazine hydrate can not be entirely restored to the pristine graphite structures. XPS and FTIR data also suggest that carbonyl and carboxyl groups can be reduced by hydrazine hydrate and possibly form hydrazone, but not a C = C structure.

  10. Temperature dependence of graphene oxide reduced by hydrazine hydrate

    NASA Astrophysics Data System (ADS)

    Ren, Peng-Gang; Yan, Ding-Xiang; Ji, Xu; Chen, Tao; Li, Zhong-Ming

    2011-02-01

    Graphene oxide (GO) was successfully prepared by a modified Hummer's method. The reduction effect and mechanism of the as-prepared GO reduced with hydrazine hydrate at different temperatures and time were characterized by x-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), x-ray diffractions (XRD), Raman spectroscopy and thermo-gravimetric analysis (TGA). The results showed that the reduction effect of GO mainly depended on treatment temperature instead of treatment time. Desirable reduction of GO can only be obtained at high treatment temperature. Reduced at 95 °C for 3 h, the C/O atomic ratio of GO increased from 3.1 to 15.1, which was impossible to obtain at low temperatures, such as 80, 60 or 15 °C, even for longer reduction time. XPS, 13C NMR and FTIR results show that most of the epoxide groups bonded to graphite during the oxidation were removed from GO and form the sp2 structure after being reduced by hydrazine hydrate at high temperature (>60 °C), leading to the electric conductivity of GO increasing from 1.5 × 10 - 6 to 5 S cm - 1, while the hydroxyls on the surface of GO were not removed by hydrazine hydrate even at high temperature. Additionally, the FTIR, XRD and Raman spectrum indicate that the GO reduced by hydrazine hydrate can not be entirely restored to the pristine graphite structures. XPS and FTIR data also suggest that carbonyl and carboxyl groups can be reduced by hydrazine hydrate and possibly form hydrazone, but not a C = C structure.

  11. Type-dependent oxidative damage in frontotemporal lobar degeneration: cortical astrocytes are targets of oxidative damage.

    PubMed

    Martínez, Anna; Carmona, Margarita; Portero-Otin, Manuel; Naudí, Alba; Pamplona, Reinald; Ferrer, Isidre

    2008-12-01

    Oxidative injury and stress responses are common features of many neurodegenerative diseases. To assess oxidative stress responses in frontotemporal lobar degeneration (FTLD), we identified increased 4-hydroxynonenal (HNE) adducts using gel electrophoresis and Western blotting in frontal cortex samples in 6 of 6 cases of FTLD with the P301L mutation in the tau gene (FTLD-tau), in 3 of 10 cases with tau-negative ubiquitin-immunoreactive inclusions, and in 2 of 3 cases associated with motor neuron disease. Selectively increased lipoxidation-derived protein damage associated with altered membrane unsaturation and fatty acid profiles was verified by mass spectrometry in FTLD-tau and FTLD associated with motor neuron disease. All FTLD-tau and most cases with increased HNE-positive bands had marked astrocytosis as determined by glial fibrillary acidic protein (GFAP) immunohistochemistry and increased GFAP expression on Western blotting; 2 FTLD cases with tau-negative ubiquitin-immunoreactive inclusions and with increased GFAP expression did not have increased HNE adducts. Bidimensional gel electrophoresis, Western blotting, in-gel digestion, and mass spectrometry identified GFAP as a major target of lipoxidation in all positive cases; confocal microscopy revealed colocalization of HNE and GFAP in cortical astrocytes, superoxide dismutase 1 in astrocytes, and superoxide dismutase 2 in astrocytes and neurons in all FTLD types. Thus, in FTLD, there is variable disease-dependent oxidative damage that is prominent in FTLD-tau, astrocytes are targets of oxidative damage, and GFAP is a target of lipoxidation. Astrocytes are, therefore, crucial elements of oxidative stress responses in FTLD.

  12. The Ehrlich-Schwoebel barrier on an oxide surface: a combined Monte-Carlo and in situ scanning tunneling microscopy approach.

    PubMed

    Gianfrancesco, Anthony G; Tselev, Alexander; Baddorf, Arthur P; Kalinin, Sergei V; Vasudevan, Rama K

    2015-11-13

    The controlled growth of epitaxial films of complex oxides requires an atomistic understanding of key parameters determining final film morphology, such as termination dependence on adatom diffusion, and height of the Ehrlich-Schwoebel (ES) barrier. Here, through an in situ scanning tunneling microscopy study of mixed-terminated La5/8Ca3/8MnO3 (LCMO) films, we image adatoms and observe pile-up at island edges. Image analysis allows determination of the population of adatoms at the edge of islands and fractions on A-site and B-site terminations. A simple Monte-Carlo model, simulating the random walk of adatoms on a sinusoidal potential landscape using Boltzmann statistics is used to reproduce the experimental data, and provides an estimate of the ES barrier as ∼0.18 ± 0.04 eV at T = 1023 K, similar to those of metal adatoms on metallic surfaces. These studies highlight the utility of in situ imaging, in combination with basic Monte-Carlo methods, in elucidating the factors which control the final film growth in complex oxides.

  13. Effect of Layer-Graded Bond Coats on Edge Stress Concentration and Oxidation Behavior of Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Ghosn, Louis J.; Miller, Robert A.

    1998-01-01

    Thermal barrier coating (TBC) durability is closely related to design, processing and microstructure of the coating Z, tn systems. Two important issues that must be considered during the design of a thermal barrier coating are thermal expansion and modulus mismatch between the substrate and the ceramic layer, and substrate oxidation. In many cases, both of these issues may be best addressed through the selection of an appropriate bond coat system. In this study, a low thermal expansion and layer-graded bond coat system, that consists of plasma-sprayed FeCoNiCrAl and FeCrAlY coatings, and a high velocity oxyfuel (HVOF) sprayed FeCrAlY coating, is developed to minimize the thermal stresses and provide oxidation resistance. The thermal expansion and oxidation behavior of the coating system are also characterized, and the strain isolation effect of the bond coat system is analyzed using the finite element method (FEM). Experiments and finite element results show that the layer-graded bond coat system possesses lower interfacial stresses. better strain isolation and excellent oxidation resistance. thus significantly improving the coating performance and durability.

  14. Pressure dependence in the methyl vinyl ketone + OH and methacrolein + OH oxidation reactions: an electronic structure study.

    PubMed

    Ochando-Pardo, Montserrat; Nebot-Gil, Ignacio; González-Lafont, Angels; Lluch, José M

    2005-08-12

    High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat more favorable than the addition processes. The subtle balance between the different pathways (additions versus abstractions) serves to give an understanding of the pressure dependence of the rate constants of these tropospheric oxidation processes.

  15. Coal tar induces AHR-dependent skin barrier repair in atopic dermatitis

    PubMed Central

    van den Bogaard, Ellen H.; Bergboer, Judith G.M.; Vonk-Bergers, Mieke; van Vlijmen-Willems, Ivonne M.J.J.; Hato, Stanleyson V.; van der Valk, Pieter G.M.; Schröder, Jens Michael; Joosten, Irma; Zeeuwen, Patrick L.J.M.; Schalkwijk, Joost

    2013-01-01

    Topical application of coal tar is one of the oldest therapies for atopic dermatitis (AD), a T helper 2 (Th2) lymphocyte–mediated skin disease associated with loss-of-function mutations in the skin barrier gene, filaggrin (FLG). Despite its longstanding clinical use and efficacy, the molecular mechanism of coal tar therapy is unknown. Using organotypic skin models with primary keratinocytes from AD patients and controls, we found that coal tar activated the aryl hydrocarbon receptor (AHR), resulting in induction of epidermal differentiation. AHR knockdown by siRNA completely abrogated this effect. Coal tar restored filaggrin expression in FLG-haploinsufficient keratinocytes to wild-type levels, and counteracted Th2 cytokine–mediated downregulation of skin barrier proteins. In AD patients, coal tar completely restored expression of major skin barrier proteins, including filaggrin. Using organotypic skin models stimulated with Th2 cytokines IL-4 and IL-13, we found coal tar to diminish spongiosis, apoptosis, and CCL26 expression, all AD hallmarks. Coal tar interfered with Th2 cytokine signaling via dephosphorylation of STAT6, most likely due to AHR-regulated activation of the NRF2 antioxidative stress pathway. The therapeutic effect of AHR activation herein described opens a new avenue to reconsider AHR as a pharmacological target and could lead to the development of mechanism-based drugs for AD. PMID:23348739

  16. Schottky barrier height switching in thin metal oxide films studied in diode and solar cell device configurations

    NASA Astrophysics Data System (ADS)

    Wing, Dahvyd; Rothschild, Avner; Tessler, Nir

    2015-08-01

    We investigate changes in the properties of 8 nm thin metal oxide (Nb-doped SrTiO3) films in response to relatively high voltage or light soaking under three Sun excitation. We measure the current-voltage behavior of metal|insulator|metal type diodes and use a device model to relate changes in device behavior to the metal oxide film properties. We find that the device's resistive switching is mainly associated with shifts (switching) of the metal oxide work function between high and low injection barrier states. The method presented here can be used for in situ monitoring of the contact work function and for quantifying the uniformity of this value across the device. We also discuss the effect of non-uniform work function on the apparent diode's ideality factor.

  17. Isothermal Oxidation Behavior of VC and Columnar Structured Thermal Barrier Coatings Deposited by Suspension Plasma Spray Technology

    NASA Astrophysics Data System (ADS)

    Li, Xiaolong; Yang, Qi; Huang, Xiao; Tang, Zhaolin

    2015-08-01

    The effects of different thermal barrier coating (TBC) top coat structures and substrate alloys on the isothermal oxidation behaviors of TBC systems were investigated at 1080 °C in lab air. The tested TBC systems consisted of two nickel-based superalloy substrates (CMSX-4 and IN738LC), a platinum aluminide bond coat and two 8YSZ top coats (vertical cracked and columnar structured). Samples with IN738LC substrate demonstrated longer isothermal oxidation lives than the counterparts with CMSX-4 substrate. Outward refractory elemental diffusion in coating systems with CMSX-4 substrate and void formation at the interface between thermally grown oxide and bond coat was found to be responsible for the early failure of TBCs. Columnar structured YSZ top coat seemed to provide better protection of the bond coating and substrate, marginally delaying the failure of the both coating systems with IN738LC and CMSX-4.

  18. Contributions of altered permeability of intestinal barrier and defecation behavior to toxicity formation from graphene oxide in nematode Caenorhabditis elegans.

    PubMed

    Wu, Qiuli; Yin, Li; Li, Xing; Tang, Meng; Zhang, Tao; Wang, Dayong

    2013-10-21

    Graphene oxide (GO) has been extensively studied for potential biomedical applications. Meanwhile, potential GO toxicity arises in both biomedical applications and non-biomedical products where environmental exposures may occur. In the present study, we examined the potential adverse effects of GO and the underlying mechanism using nematode Caenorhabditis elegans as the assay system. We compared the in vivo effects of GO between acute exposure and prolonged exposure, and found that prolonged exposure to 0.5-100 mg L(-1) of GO caused damage on functions of both primary (intestine) and secondary (neuron and reproductive organ) targeted organs. In the intestine, ROS production was significantly correlated with the formation of adverse effects on functions of both primary and secondary targeted organs. GO could be translocated into intestinal cells with loss of microvilli, and distributed to be adjacent to or surrounding mitochondria. Prolonged exposure to GO resulted in a hyper-permeable state of the intestinal barrier, an increase in mean defecation cycle length, and alteration of genes required for intestinal development and defecation behavior. Thus, our data suggest that prolonged exposure to GO may cause potential risk to environmental organisms after release into the environment. GO toxicity may be due to the combinational effects of oxidative stress in the intestinal barrier, enhanced permeability of the biological barrier, and suppressed defecation behavior in C. elegans.

  19. Surface plasmon resonance measurement of AlOx insulating barriers in magnetic tunnel junctions formed by remote rf plasma oxidation process

    NASA Astrophysics Data System (ADS)

    Park, J. H.; Yoon, K. S.; Yang, J. Y.; Kim, E. K.; Lee, C. H.; Kim, C. O.; Hong, J. P.

    2002-09-01

    A surface plasmon resonance spectroscopy (SPRS) measurement was carried out to determine dielectric properties, oxidation states, and optimum thickness of AlOx insulating barrier in magnetic tunnel junctions. The insulating barriers were prepared as a function of oxidation time by using a remote rf plasma oxidation process. The experimental results revealed that the dielectric value and optimum thickness of the AlOx insulating barrier in our junctions were found to be 1.79+i1.77 and 11.26 A, respectively. For comparison, the magnetic tunneling junction was also fabricated using the same oxidation condition. The best magneto-resistance ratio of about 34% was observed at an optimum oxidation time of 70 s, as expected by the SPRS measurement.

  20. Oxidation resistance of Al2O3-nanostructured/CSZ composite compared to conventional CSZ and YSZ thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Keyvani, A.; Bahamirian, M.

    2016-10-01

    Thermal barrier coatings are widely used in combustion sections of turbine engines, however, their main disadvantage is the spallation from the bond coat, occurring due to oxidation and formation of thermally grown oxide (TGO). In this paper, the oxidation resistance of yttria stabilized zirconia (YSZ), ceria stabilized zirconia (CSZ), and Al2O3-nanostructured/CSZ composite coatings have been studied and compared with each other. Samples were heated in air at 1100 °C using an electrical furnace. Three types of the top coats were applied by thermal spray technique on IN738LC base metal. Scanning electron microscopy was used to study the microstructure of the coatings before and after the oxidation. The experimental results showed that Al2O3-nanostructured/CSZ composite coating exhibits considerably better oxidation resistance compared to conventional YSZ and CSZ coatings. The microstructural analysis indicated a smaller growth of TGO in the Al2O3-nanostructured/CSZ composite coating, improving the oxidation resistance of the coating.

  1. The Effect of Interface Roughness and Oxide Film Thickness on the Inelastic Response of Thermal Barrier Coatings to Thermal Cycling

    NASA Technical Reports Server (NTRS)

    Pindera, Marek-Jerzy; Aboudi, Jacob; Arnold, Steven M.

    1999-01-01

    The effects of interfacial roughness and oxide film thickness on thermally-induced stresses in plasma-sprayed thermal barrier coatings subjected to thermal cycling are investigated using the recently developed higher-order theory for functionally graded materials. The higher-order theory is shown to be a viable alternative to the finite-element approach, capable of modeling different interfacial roughness architectures in the presence of an aluminum oxide layer and capturing the high stress gradients that occur at the top coat/bond coat interface. The oxide layer thickness is demonstrated to have a substantially greater effect on the evolution of residual stresses than local variations in interfacial roughness. Further, the location of delamination initiation in the top coat is predicted to change with increasing oxide layer thickness. This result can be used to optimize the thickness of a pre-oxidized layer introduced at the top coat/bond coat interface in order to enhance TBC durability as suggested by some researchers. The results of our investigation also support a recently proposed hypothesis regarding delamination initiation and propagation in the presence of an evolving bond coat oxidation, while pointing to the importance of interfacial roughness details and specimen geometry in modeling this phenomenon.

  2. Patient-centered Care to Address Barriers for Pregnant Women with Opioid Dependence.

    PubMed

    Sutter, Mary Beth; Gopman, Sarah; Leeman, Lawrence

    2017-03-01

    Pregnant women affected by substance use often encounter barriers to treatment, including housing insecurity, poverty, mental health issues, social stigma, and access to health care. Providers may lack the resources needed to provide quality care. Clinicians offering prenatal care to women with substance use disorder are encouraged to support family-centered, multidisciplinary care to women and their infants, focusing on harm reduction. Collaboration between providers of maternity care, substance abuse treatment, case management, family primary care, and pediatric developmental care can improve outcomes during pregnancy and through the early years of parenting.

  3. Stress dependent oxidation of sputtered niobium and effects on superconductivity

    SciTech Connect

    David Henry, M. Wolfley, Steve; Monson, Todd; Clark, Blythe G.; Shaner, Eric; Jarecki, Robert

    2014-02-28

    We report on the suppression of room temperature oxidation of DC sputtered niobium films and the effects upon the superconductive transition temperature, T{sub c}. Niobium was sputter-deposited on silicon dioxide coated 150 mm wafers and permitted to oxidize at room temperature and pressure for up to two years. Resistivity and stress measurements indicate that tensile films greater than 400 MPa resist bulk oxidation with measurements using transmission electron microscope, electron dispersive X-ray spectroscopy, x-ray photoelectric spectroscopy, and secondary ion mass spectrometry confirming this result. Although a surface oxide, Nb{sub 2}O{sub 5}, consumed the top 6–10 nm, we measure less than 1 at. % oxygen and nitrogen in the bulk of the films after the oxidation period. T{sub c} measurements using a SQUID magnetometer indicate that the tensile films maintained a T{sub c} approaching the dirty superconductive limit of 8.4 K after two years of oxidation while maintaining room temperature sheet resistance. This work demonstrates that control over niobium film stress during deposition can prevent bulk oxidation by limiting the vertical grain boundaries ability to oxidize, prolonging the superconductive properties of sputtered niobium when exposed to atmosphere.

  4. Dependence of riverine nitrous oxide emissions on dissolved oxygen levels

    NASA Astrophysics Data System (ADS)

    Rosamond, Madeline S.; Thuss, Simon J.; Schiff, Sherry L.

    2012-10-01

    Nitrous oxide is a potent greenhouse gas, and it destroys stratospheric ozone. Seventeen per cent of agricultural nitrous oxide emissions come from the production of nitrous oxide in streams, rivers and estuaries, in turn a result of inorganic nitrogen input through leaching, runoff and sewage. The Intergovernmental Panel on Climate Change and global nitrous oxide budgets assume that riverine nitrous oxide emissions increase linearly with dissolved inorganic nitrogen loads, but data are sparse and conflicting. Here we report measurements over two years of nitrous oxide emissions in the Grand River, Canada, a seventh-order temperate river that is affected by agricultural runoff and outflow from a waste-water treatment plant. Emissions were disproportionately high in urban areas and during nocturnal summer periods. Moreover, annual emission estimates that are based on dissolved inorganic nitrogen loads overestimated the measured emissions in a wet year and underestimated them in a dry year. We found no correlations of nitrous oxide emissions with nitrate or dissolved inorganic nitrogen, but detected negative correlations with dissolved oxygen, suggesting that nitrate concentrations did not limit emissions. We conclude that future increases in nitrate export to rivers will not necessarily lead to higher nitrous oxide emissions, but more widespread hypoxia most likely will.

  5. PH Dependent Interactions between Aqueous Iodide Ion and Selected Oxidizers.

    DTIC Science & Technology

    1985-12-06

    COSATI CODES I&. SUBJECT IERMS (Continue an evven d mocesaey and idoetfy by 510&k number) C’ ELD GROUP SUB-ROUP >Oxidize Iodometry Titration Oxidation... iodometry : hypochlorite interacts instantly with iodide ion. However, a kinetically rapid decon reaction may not be best for all possible situations. An

  6. Stress dependent oxidation of sputtered niobium and effects on superconductivity

    NASA Astrophysics Data System (ADS)

    David Henry, M.; Wolfley, Steve; Monson, Todd; Clark, Blythe G.; Shaner, Eric; Jarecki, Robert

    2014-02-01

    We report on the suppression of room temperature oxidation of DC sputtered niobium films and the effects upon the superconductive transition temperature, Tc. Niobium was sputter-deposited on silicon dioxide coated 150 mm wafers and permitted to oxidize at room temperature and pressure for up to two years. Resistivity and stress measurements indicate that tensile films greater than 400 MPa resist bulk oxidation with measurements using transmission electron microscope, electron dispersive X-ray spectroscopy, x-ray photoelectric spectroscopy, and secondary ion mass spectrometry confirming this result. Although a surface oxide, Nb2O5, consumed the top 6-10 nm, we measure less than 1 at. % oxygen and nitrogen in the bulk of the films after the oxidation period. Tc measurements using a SQUID magnetometer indicate that the tensile films maintained a Tc approaching the dirty superconductive limit of 8.4 K after two years of oxidation while maintaining room temperature sheet resistance. This work demonstrates that control over niobium film stress during deposition can prevent bulk oxidation by limiting the vertical grain boundaries ability to oxidize, prolonging the superconductive properties of sputtered niobium when exposed to atmosphere.

  7. Geochemical controls on microbial nitrate-dependent U(IV) oxidation

    USGS Publications Warehouse

    Senko, John M.; Suflita, Joseph M.; Krumholz, Lee R.

    2005-01-01

    After reductive immobilization of uranium, the element may be oxidized and remobilized in the presence of nitrate by the activity of dissimilatory nitrate-reducing bacteria. We examined controls on microbially mediated nitrate-dependent U(IV) oxidation in landfill leachate-impacted subsurface sediments. Nitrate-dependent U(IV)-oxidizing bacteria were at least two orders of magnitude less numerous in these sediments than glucose- or Fe(II)-oxidizing nitrate-reducing bacteria and grew more slowly than the latter organisms, suggesting that U(IV) is ultimately oxidized by Fe(III) produced by nitrate-dependent Fe(II)-oxidizing bacteria or by oxidation of Fe(II) by nitrite that accumulates during organotrophic dissimilatory nitrate reduction. We examined the effect of nitrate and reductant concentration on nitrate-dependent U(IV) oxidation in sediment incubations and used the initial reductive capacity (RDC = [reducing equivalents] - [oxidizing equivalents]) of the incubations as a unified measurement of the nitrate or reductant concentration. When we lowered the RDC with progressively higher nitrate concentrations, we observed a corresponding increase in the extent of U(IV) oxidation, but did not observe this relationship between RDC and U(IV) oxidation rate, especially when RDC > 0, suggesting that nitrate concentration strongly controls the extent, but not the rate of nitrate-dependent U(IV) oxidation. On the other hand, when we raised the RDC in sediment incubations with progressively higher reductant (acetate, sulfide, soluble Fe(II), or FeS) concentrations, we observed progressively lower extents and rates of nitrate-dependent U(IV) oxidation. Acetate was a relatively poor inhibitor of nitrate-dependent U(IV) oxidation, while Fe(II) was the most effective inhibitor. Based on these results, we propose that it may be possible to predict the stability of U(IV) in a bioremediated aquifer based on the geochemical characteristics of that aquifer.

  8. Schottky barrier height reduction for holes by Fermi level depinning using metal/nickel oxide/silicon contacts

    SciTech Connect

    Islam, Raisul Shine, Gautam; Saraswat, Krishna C.

    2014-11-03

    We report the experimental demonstration of Fermi level depinning using nickel oxide (NiO) as the insulator material in metal-insulator-semiconductor (M-I-S) contacts. Using this contact, we show less than 0.1 eV barrier height for holes in platinum/NiO/silicon (Pt/NiO/p-Si) contact. Overall, the pinning factor was improved from 0.08 (metal/Si) to 0.26 (metal/NiO/Si). The experimental results show good agreement with that obtained from theoretical calculation. NiO offers high conduction band offset and low valence band offset with Si. By reducing Schottky barrier height, this contact can be used as a carrier selective contact allowing hole transport but blocking electron transport, which is important for high efficiency in photonic applications such as photovoltaics and optical detectors.

  9. Commensal Bacteria-Dependent Indole Production Enhances Epithelial Barrier Function in the Colon

    PubMed Central

    Shimada, Yosuke; Kinoshita, Makoto; Harada, Kazuo; Mizutani, Masafumi; Masahata, Kazunori; Kayama, Hisako; Takeda, Kiyoshi

    2013-01-01

    Microbiota have been shown to have a great influence on functions of intestinal epithelial cells (ECs). The role of indole as a quorum-sensing (QS) molecule mediating intercellular signals in bacteria has been well appreciated. However, it remains unknown whether indole has beneficial effects on maintaining intestinal barriers in vivo. In this study, we analyzed the effect of indole on ECs using a germ free (GF) mouse model. GF mice showed decreased expression of junctional complex molecules in colonic ECs. The feces of specific pathogen-free (SPF) mice contained a high amount of indole; however the amount was significantly decreased in the feces of GF mice by 27-fold. Oral administration of indole-containing capsules resulted in increased expression of both tight junction (TJ)- and adherens junction (AJ)-associated molecules in colonic ECs in GF mice. In accordance with the increased expression of these junctional complex molecules, GF mice given indole-containing capsules showed higher resistance to dextran sodium sulfate (DSS)-induced colitis. A similar protective effect of indole on DSS-induced epithelial damage was also observed in mice bred in SPF conditions. These findings highlight the beneficial role of indole in establishing an epithelial barrier in vivo. PMID:24278294

  10. Potential of Lactobacillus plantarum CCFM639 in Protecting against Aluminum Toxicity Mediated by Intestinal Barrier Function and Oxidative Stress

    PubMed Central

    Yu, Leilei; Zhai, Qixiao; Tian, Fengwei; Liu, Xiaoming; Wang, Gang; Zhao, Jianxin; Zhang, Hao; Narbad, Arjan; Chen, Wei

    2016-01-01

    Aluminum (Al) is a ubiquitous metal that can seriously harm the health of animals and humans. In our previous study, we demonstrated that Lactobacillus plantarum CCFM639 can decrease Al burden in the tissues of mice by inhibiting intestinal Al absorption. The main aim of the present research was to investigate whether the protection by the strain is also associated with enhancement of the intestinal barrier, alleviation of oxidative stress and modulation of the inflammatory response. In an in vitro cell model, two protection modes (intervention and therapy) were examined and the results indicated that L. plantarum CCFM639 alleviated Al-induced cytotoxicity. In a mouse model, L. plantarum CCFM639 treatment was found to significantly alleviate oxidative stress in the intestinal tract, regulate the function of the intestinal mucosal immune system, restore the integrity of tight junction proteins and maintain intestinal permeability. These results suggest that in addition to Al sequestration, L. plantarum CCFM639 can also inhibit Al absorption by protecting the intestinal barrier, alleviating Al-induced oxidative stress and inflammatory response. Therefore, L. plantarum CCFM639 has the potential to be a dietary supplement ingredient that provides protection against Al-induced gut injury. PMID:27918411

  11. Potential of Lactobacillus plantarum CCFM639 in Protecting against Aluminum Toxicity Mediated by Intestinal Barrier Function and Oxidative Stress.

    PubMed

    Yu, Leilei; Zhai, Qixiao; Tian, Fengwei; Liu, Xiaoming; Wang, Gang; Zhao, Jianxin; Zhang, Hao; Narbad, Arjan; Chen, Wei

    2016-12-02

    Aluminum (Al) is a ubiquitous metal that can seriously harm the health of animals and humans. In our previous study, we demonstrated that Lactobacillus plantarum CCFM639 can decrease Al burden in the tissues of mice by inhibiting intestinal Al absorption. The main aim of the present research was to investigate whether the protection by the strain is also associated with enhancement of the intestinal barrier, alleviation of oxidative stress and modulation of the inflammatory response. In an in vitro cell model, two protection modes (intervention and therapy) were examined and the results indicated that L. plantarum CCFM639 alleviated Al-induced cytotoxicity. In a mouse model, L. plantarum CCFM639 treatment was found to significantly alleviate oxidative stress in the intestinal tract, regulate the function of the intestinal mucosal immune system, restore the integrity of tight junction proteins and maintain intestinal permeability. These results suggest that in addition to Al sequestration, L. plantarum CCFM639 can also inhibit Al absorption by protecting the intestinal barrier, alleviating Al-induced oxidative stress and inflammatory response. Therefore, L. plantarum CCFM639 has the potential to be a dietary supplement ingredient that provides protection against Al-induced gut injury.

  12. Temperature-dependent bias-stress-induced electrical instability of amorphous indium-gallium-zinc-oxide thin-film transistors

    NASA Astrophysics Data System (ADS)

    Qian, Hui-Min; Yu, Guang; Lu, Hai; Wu, Chen-Fei; Tang, Lan-Feng; Zhou, Dong; Ren, Fang-Fang; Zhang, Rong; Zheng, You-Liao; Huang, Xiao-Ming

    2015-07-01

    The time and temperature dependence of threshold voltage shift under positive-bias stress (PBS) and the following recovery process are investigated in amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistors. It is found that the time dependence of threshold voltage shift can be well described by a stretched exponential equation in which the time constant τ is found to be temperature dependent. Based on Arrhenius plots, an average effective energy barrier Eτstress = 0.72 eV for the PBS process and an average effective energy barrier Eτrecovery = 0.58 eV for the recovery process are extracted respectively. A charge trapping/detrapping model is used to explain the threshold voltage shift in both the PBS and the recovery process. The influence of gate bias stress on transistor performance is one of the most critical issues for practical device development. Project supported by the National Basic Research Program of China (Grant Nos. 2011CB301900 and 2011CB922100) and the Priority Academic Program Development of Jiangsu Higher Education Institutions, China

  13. Propionate Ameliorates Dextran Sodium Sulfate-Induced Colitis by Improving Intestinal Barrier Function and Reducing Inflammation and Oxidative Stress

    PubMed Central

    Tong, Ling-chang; Wang, Yue; Wang, Zhi-bin; Liu, Wei-ye; Sun, Sheng; Li, Ling; Su, Ding-feng; Zhang, Li-chao

    2016-01-01

    Propionate is a short chain fatty acid that is abundant as butyrate in the gut and blood. However, propionate has not been studied as extensively as butyrate in the treatment of colitis. The present study was to investigate the effects of sodium propionate on intestinal barrier function, inflammation and oxidative stress in dextran sulfate sodium (DSS)-induced colitis mice. Animals in DSS group received drinking water from 1 to 6 days and DSS [3% (w/v) dissolved in double distilled water] instead of drinking water from 7 to 14 days. Animals in DSS+propionate (DSS+Prop) group were given 1% sodium propionate for 14 consecutive days and supplemented with 3% DSS solution on day 7–14. Intestinal barrier function, proinflammatory factors, oxidative stress, and signal transducer and activator of transcription 3 (STAT3) signaling pathway in the colon were determined. It was found that sodium propionate ameliorated body weight loss, colon-length shortening and colonic damage in colitis mice. Sodium propionate significantly inhibited the increase of FITC-dextran in serum and the decrease of zonula occludens-1 (ZO-1), occludin, and E-cadherin expression in the colonic tissue. It also inhibited the expression of interleukin (IL)-1β, IL-6, and tumor necrosis factor-α (TNF-α) mRNA and phosphorylation of STAT3 in colitis mice markedly, reduced the myeloperoxidase (MPO) level, and increased the superoxide dismutase and catalase level in colon and serum compared with DSS group. Sodium propionate inhibited macrophages with CD68 marker infiltration into the colonic mucosa of colitis mice. These results suggest that oral administration of sodium propionate could ameliorate DSS-induced colitis mainly by improving intestinal barrier function and reducing inflammation and oxidative stress via the STAT3 signaling pathway. PMID:27574508

  14. Effect of barrier properties of zein colloidal particles and oil-in-water emulsions on oxidative stability of encapsulated bioactive compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oxidation of encapsulated bioactive compounds is a key challenge that limits shelf-life of bioactive containing products. The objectives of this study were to compare differences between the oxidative barrier properties of biopolymer particle based encapsulation system (zein colloidal particles) and...

  15. Metabolically dependent blood-brain barrier breakdown in chronic relapsing experimental allergic encephalomyelitis.

    PubMed

    Hawkins, C P; Munro, P M; Landon, D N; McDonald, W I

    1992-01-01

    We have studied chronic relapsing experimental allergic encephalomyelitis (CREAE), a model of immune-mediated demyelination, using gadolinium (Gd)-enhanced magnetic resonance imaging in vivo and the blood-brain barrier (BBB) markers, lanthanum nitrate and Gd nitrate, histologically. In regions of the spinal cord showing Gd enhancement, there was evidence for vesicular transport as a mechanism of BBB breakdown in CREAE, shown by an increased number of endothelial vesicles containing lanthanide (lanthanum or Gd, whichever had been perfused) and deposition of tracer in the perivascular space; tight interendothelial junctions remained intact. Prior perfusion with 2,4-dinitrophenol, a metabolic inhibitor, suppressed the appearance of endothelial vesicles containing lanthanide and tracer in the perivascular space. We conclude that an important contribution to BBB breakdown in CREAE is mediated by a metabolic change in the endothelial cells associated with increased vesicular transport.

  16. Thermal barrier coating life and isothermal oxidation of low-pressure plasma-sprayed bond coat alloys

    NASA Technical Reports Server (NTRS)

    Brindley, W. J.; Miller, R. A.

    1990-01-01

    The paper investigates the isothermal oxidation kinetics of Ni-35Cr-6Al-0.95Y, Ni-18Cr-12Al-0.3Y, and Ni-16Cr-6Al-0.3Y low-pressure plasma-sprayed bond coat alloys and examines the effect of these alloys on the thermal barrier coating (TBC) cyclic life. TBC life was examined by cycling substrates coated with the different bond coats and a ZrO2-7 wt pct Y2O3 TBC in an air-rich burner rig flame between 1150 C and room temperature. The oxidation kinetics of the three bond coat alloys was examined by isothermal oxidation of monolithic NJiCrAlY coupons at 1083 C. The Ni-35Cr-6Al-0.95Y alloy exhibits comparatively high isothermal oxidation weight gains and provides the longest TBC life, whereas the Ni-16Cr-6Al-0.3Y alloy had the lowest weight gains and provided the shortest TBC life. The results show that, although bond coat oxidation is known to have a strong detrimental effect on TBC life, it is not the only bond coat factor that determines TBC life.

  17. Temperature-dependent hydration at micellar surface: activation energy barrier crossing model revisited.

    PubMed

    Mitra, Rajib Kumar; Sinha, Sudarson Sekhar; Pal, Samir Kumar

    2007-07-05

    In recent years, the validity of the activation energy barrier crossing model at the micellar surface brings notable controversy (Sen, P.; Mukherjee, S.; Halder, A.; Bhattacharyya, K. Chem. Phys. Lett. 2004, 385, 357-361. Kumbhakar, M.; Goel, T.; Mukherjee, T.; Pal, H. J. Phys. Chem. B 2004, 108, 19246-19254.) in the literature. In order to check the validity of the model by time-resolved solvation of a probe fluorophore, a wider range of temperature must be considered. At the same time, spatial heterogeneity (solubilization) of the probe and structural perturbation of the host micelle should carefully be avoided, which was not strictly maintained in the earlier studies. We report here the solvation dynamics of 4-(dicyanomethylene)-2-methyl-6(p-dimethylamino-styryl) 4H-pyran (DCM) in the SDS micelle at 298, 323, and 348 K. The probe DCM is completely insoluble in bulk water in this wide range of temperature. The size of the micelle at different temperatures using the dynamic light scattering (DLS) technique is found to have insignificant change. The hydration number of the micelle, determined by sound velocity measurements, decreases with increasing temperature. Time-resolved fluorescence anisotropy reveals the retention of the probe in the micellar interface within the temperature range. The average solvation time decreases with increasing temperature. The result of the solvation study has been analyzed in the light of energetics of bound to free water conversion at a constant size and decreasing hydration number at the micellar surface. The solvation process at the micellar surface has been found to be the activation energy barrier crossing type, in which interfacially bound type water molecules get converted into free type molecules. We have calculated Ea to be 3.5 kcal mol-1, which is in good agreement with that obtained by molecular dynamics simulation studies.

  18. Probiotics ameliorate the hydrogen peroxide-induced epithelial barrier disruption by a PKC- and MAP kinase-dependent mechanism

    PubMed Central

    Seth, A.; Yan, Fang; Polk, D.Brent; Rao, R. K.

    2009-01-01

    Probiotics promote intestinal epithelial integrity and reduce infection and diarrhea. We evaluated the effect of Lactobacillus rhamnosus GG-produced soluble proteins (p40 and p75) on the hydrogen peroxide-induced disruption of tight junctions and barrier function in Caco-2 cell monolayers. Pretreatment of cell monolayers with p40 or p75 attenuated the hydrogen peroxide-induced decrease in transepithelial resistance and increase in inulin permeability in a time- and dose-dependent manner. p40 and p75 also prevented hydrogen peroxide-induced redistribution of occludin, ZO-1, E-cadherin, and β-catenin from the intercellular junctions and their dissociation from the detergent-insoluble fractions. Both p40 and p75 induced a rapid increase in the membrane translocation of PKCβI and PKCε. The attenuation of hydrogen peroxide-induced inulin permeability and redistribution of tight junction proteins by p40 and p75 was abrogated by Ro-32-0432, a PKC inhibitor. p40 and p75 also rapidly increased the levels of phospho-ERK1/2 in the detergent-insoluble fractions. U0126 (a MAP kinase inhibitor) attenuated the p40- and p75-mediated reduction of hydrogen peroxide-induced tight junction disruption and inulin permeability. These studies demonstrate that probiotic-secretory proteins protect the intestinal epithelial tight junctions and the barrier function from hydrogen peroxide-induced insult by a PKC- and MAP kinase-dependent mechanism. PMID:18292183

  19. Probiotics ameliorate the hydrogen peroxide-induced epithelial barrier disruption by a PKC- and MAP kinase-dependent mechanism.

    PubMed

    Seth, A; Yan, Fang; Polk, D Brent; Rao, R K

    2008-04-01

    Probiotics promote intestinal epithelial integrity and reduce infection and diarrhea. We evaluated the effect of Lactobacillus rhamnosus GG-produced soluble proteins (p40 and p75) on the hydrogen peroxide-induced disruption of tight junctions and barrier function in Caco-2 cell monolayers. Pretreatment of cell monolayers with p40 or p75 attenuated the hydrogen peroxide-induced decrease in transepithelial resistance and increase in inulin permeability in a time- and dose-dependent manner. p40 and p75 also prevented hydrogen peroxide-induced redistribution of occludin, ZO-1, E-cadherin, and beta-catenin from the intercellular junctions and their dissociation from the detergent-insoluble fractions. Both p40 and p75 induced a rapid increase in the membrane translocation of PKCbetaI and PKCepsilon. The attenuation of hydrogen peroxide-induced inulin permeability and redistribution of tight junction proteins by p40 and p75 was abrogated by Ro-32-0432, a PKC inhibitor. p40 and p75 also rapidly increased the levels of phospho-ERK1/2 in the detergent-insoluble fractions. U0126 (a MAP kinase inhibitor) attenuated the p40- and p75-mediated reduction of hydrogen peroxide-induced tight junction disruption and inulin permeability. These studies demonstrate that probiotic-secretory proteins protect the intestinal epithelial tight junctions and the barrier function from hydrogen peroxide-induced insult by a PKC- and MAP kinase-dependent mechanism.

  20. Characterization of aluminum oxide tunnel barriers by combining transport measurements and transmission electron microscopy imaging

    SciTech Connect

    Aref, T.; Averin, A.; Nguyend, H. Q.; Pekola, J. P.; Dijken, S. van; Yao, L. D.; Ferring, A.; Koberidze, M.; Nieminen, R. M.

    2014-08-21

    We present two approaches for studying the uniformity of a tunnel barrier. The first approach is based on measuring single-electron and two-electron tunneling in a hybrid single-electron transistor. Our measurements indicate that the effective area of a conduction channel is about one order of magnitude larger than predicted by theoretical calculations. With the second method, transmission electron microscopy, we demonstrate that variations in the barrier thickness are a plausible explanation for the larger effective area and an enhancement of higher order tunneling processes.

  1. ALD grown bilayer junction of ZnO:Al and tunnel oxide barrier for SIS solar cell☆

    PubMed Central

    Bethge, O.; Nobile, M.; Abermann, S.; Glaser, M.; Bertagnolli, E.

    2013-01-01

    Various metal oxides are probed as extrinsic thin tunnel barriers in Semiconductor Insulator Semiconductor solar cells. Namely Al2O3, ZrO2, Y2O3, and La2O3 thin films are in between n-type ZnO:Al (AZO) and p-type Si substrates by means of Atomic Layer Deposition. Low reverse dark current–density as low as 3×10−7 A/cm2, a fill factor up to 71.3%, and open-circuit voltage as high as 527 mV are obtained, achieving conversion efficiency of 8% for the rare earth oxide La2O3. ZrO2 and notably Al2O3 show drawbacks in performance suggesting an adverse reactivity with AZO as also indicated by X-ray Photoelectron Spectroscopy. PMID:26877596

  2. Size-dependent magnetic properties of iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Patsula, Vitalii; Moskvin, Maksym; Dutz, Silvio; Horák, Daniel

    2016-01-01

    Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.

  3. Borate cross-linking chitosan/graphene oxide films: Toward the simultaneous enhancement of gases barrier and mechanical properties

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Capezzuto, Filomena; Buonocore, Giovanna G.; Tescione, Fabiana; Lavorgna, Marino; Xia, Hesheng; Ambrosio, Luigi

    2015-12-01

    Borate adducts, originated from hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan (CS) and graphene oxide (GO) nanosheets for the production of innovative composite sustainable materials. CS/GO film consisting of 10wt% borax and 1wt% GO exhibits a significant improvement of both toughness and oxygen barrier properties in comparison to pristine chitosan. In particular the tensile strength increases by about 100% and 150% after thermal annealing of samples at 90°C for 50min whereas the oxygen permeability reduces of about 90% compared to pristine chitosan. The enhancement of both mechanical and barrier properties is ascribed to the formation of a resistant network due to the chemical crosslinking, including borate orthoester bonds and hydroxyl moieties complexes, formed among borate ions, chitosan, and GO nanoplatelets. The crosslinked graphene-based chitosan material with its enhanced mechanical and barrier properties may significantly broad the range of applications of chitosan based-materials which presently are very limited and addressed only to packaging.

  4. Annealing of CoFeB/MgO based single and double barrier magnetic tunnel junctions: Tunnel magnetoresistance, bias dependence, and output voltage

    NASA Astrophysics Data System (ADS)

    Feng, G.; van Dijken, Sebastiaan; Feng, J. F.; Coey, J. M. D.; Leo, T.; Smith, David J.

    2009-02-01

    Co40Fe40B20/MgO single and double barrier magnetic tunnel junctions (MTJs) were grown using target-facing-target sputtering for MgO barriers and conventional dc magnetron sputtering for Co40Fe40B20 ferromagnetic electrodes. Large tunnel magnetoresistance (TMR) ratios, 230% for single barrier MTJs and 120% for the double barrier MTJs, were obtained after postdeposition annealing in a field of 800 mT. The lower TMR ratio for double barrier MTJs can be attributed to the amorphous nature of the middle Co40Fe40B20 free layer, which could not be crystallized during postannealing. A highly asymmetric bias voltage dependence of the TMR can be observed for both single and double barrier MTJs in the as-deposited states and after field annealing at low temperature. The asymmetry decreases with increasing annealing temperature and the bias dependence becomes almost symmetric after annealing at 350 °C. Maximum output voltages of 0.65 and 0.85 V were obtained for both single and double barrier MTJs, respectively, after annealing at 300 °C, a temperature which is high enough for large TMR ratios but insufficient to completely remove asymmetry from the TMR bias dependence.

  5. Capturing local atomic environment dependence of activation barriers in metals using cluster expansion models

    NASA Astrophysics Data System (ADS)

    Kulkarni, Nimish; Chatterjee, Abhijit

    2016-10-01

    It is well known that surface diffusion in metals can proceed via multiple mechanisms, such as hop, exchange and other types of concerted moves. However, the manner in which kinetic rates associated with a mechanism can depend sensitively on local atomic environment is relatively less understood. We describe recent attempts in our research group to capture the atomic environment dependence using the cluster expansion model (CEM). In particular, we focus on hop and exchange moves at the (001) surface in homoepitaxy, and show that while CEM can work remarkably well in most cases, it can sometimes provide inaccurate predictions for concerted moves.

  6. Good genes, oxidative stress and condition-dependent sexual signals.

    PubMed Central

    von Schantz, T; Bensch, S; Grahn, M; Hasselquist, D; Wittzell, H

    1999-01-01

    The immune and the detoxication systems of animals are characterized by allelic polymorphisms, which underlie individual differences in ability to combat assaults from pathogens and toxic compounds. Previous studies have shown that females may improve offspring survival by selecting mates on the basis of sexual ornaments and signals that honestly reveal health. In many cases the expression of these ornaments appears to be particularly sensitive to oxidative stress. Activated immune and detoxication systems often generate oxidative stress by an extensive production of reactive metabolites and free radicals. Given that tolerance or resistance to toxic compounds and pathogens can be inherited, female choice should promote the evolution of male ornaments that reliably reveal the status of the bearers' level of oxidative stress. Hence, oxidative stress may be one important agent linking the expression of sexual ornaments to genetic variation in fitness-related traits, thus promoting the evolution of female mate choice and male sexual ornamentation, a controversial issue in evolutionary biology ever since Darwin. PMID:10081154

  7. A dielectric barrier discharge terminally inactivates RNase A by oxidizing sulfur-containing amino acids and breaking structural disulfide bonds

    NASA Astrophysics Data System (ADS)

    Lackmann, J.-W.; Baldus, S.; Steinborn, E.; Edengeiser, E.; Kogelheide, F.; Langklotz, S.; Schneider, S.; Leichert, L. I. O.; Benedikt, J.; Awakowicz, P.; Bandow, J. E.

    2015-12-01

    RNases are among the most stable proteins in nature. They even refold spontaneously after heat inactivation, regaining full activity. Due to their stability and universal presence, they often pose a problem when experimenting with RNA. We investigated the capabilities of nonthermal atmospheric-pressure plasmas to inactivate RNase A and studied the inactivation mechanism on a molecular level. While prolonged heating above 90 °C is required for heat inactivating RNase A, direct plasma treatment with a dielectric barrier discharge (DBD) source caused permanent inactivation within minutes. Circular dichroism spectroscopy showed that DBD-treated RNase A unfolds rapidly. Raman spectroscopy indicated methionine modifications and formation of sulfonic acid. A mass spectrometry-based analysis of the protein modifications that occur during plasma treatment over time revealed that methionine sulfoxide formation coincides with protein inactivation. Chemical reduction of methionine sulfoxides partially restored RNase A activity confirming that sulfoxidation is causal and sufficient for RNase A inactivation. Continued plasma exposure led to over-oxidation of structural disulfide bonds. Using antibodies, disulfide bond over-oxidation was shown to be a general protein inactivation mechanism of the DBD. The antibody’s heavy and light chains linked by disulfide bonds dissociated after plasma exposure. Based on their ability to inactivate proteins by oxidation of sulfur-containing amino acids and over-oxidation of disulfide bonds, DBD devices present a viable option for inactivating undesired or hazardous proteins on heat or solvent-sensitive surfaces.

  8. Neuropsychiatric disease relevance of circulating anti-NMDA receptor autoantibodies depends on blood-brain barrier integrity.

    PubMed

    Hammer, C; Stepniak, B; Schneider, A; Papiol, S; Tantra, M; Begemann, M; Sirén, A-L; Pardo, L A; Sperling, S; Mohd Jofrry, S; Gurvich, A; Jensen, N; Ostmeier, K; Lühder, F; Probst, C; Martens, H; Gillis, M; Saher, G; Assogna, F; Spalletta, G; Stöcker, W; Schulz, T F; Nave, K-A; Ehrenreich, H

    2014-10-01

    In 2007, a multifaceted syndrome, associated with anti-NMDA receptor autoantibodies (NMDAR-AB) of immunoglobulin-G isotype, has been described, which variably consists of psychosis, epilepsy, cognitive decline and extrapyramidal symptoms. Prevalence and significance of NMDAR-AB in complex neuropsychiatric disease versus health, however, have remained unclear. We tested sera of 2817 subjects (1325 healthy, 1081 schizophrenic, 263 Parkinson and 148 affective-disorder subjects) for presence of NMDAR-AB, conducted a genome-wide genetic association study, comparing AB carriers versus non-carriers, and assessed their influenza AB status. For mechanistic insight and documentation of AB functionality, in vivo experiments involving mice with deficient blood-brain barrier (ApoE(-/-)) and in vitro endocytosis assays in primary cortical neurons were performed. In 10.5% of subjects, NMDAR-AB (NR1 subunit) of any immunoglobulin isotype were detected, with no difference in seroprevalence, titer or in vitro functionality between patients and healthy controls. Administration of extracted human serum to mice influenced basal and MK-801-induced activity in the open field only in ApoE(-/-) mice injected with NMDAR-AB-positive serum but not in respective controls. Seropositive schizophrenic patients with a history of neurotrauma or birth complications, indicating an at least temporarily compromised blood-brain barrier, had more neurological abnormalities than seronegative patients with comparable history. A common genetic variant (rs524991, P=6.15E-08) as well as past influenza A (P=0.024) or B (P=0.006) infection were identified as predisposing factors for NMDAR-AB seropositivity. The >10% overall seroprevalence of NMDAR-AB of both healthy individuals and patients is unexpectedly high. Clinical significance, however, apparently depends on association with past or present perturbations of blood-brain barrier function.

  9. Scattering of surface plasmon polaritons by impedance barriers: Dependence on angle of incidence

    NASA Astrophysics Data System (ADS)

    Nikitin, A. Yu.; Brucoli, G.; García-Vidal, F. J.; Martín-Moreno, L.

    2008-05-01

    This paper studies theoretically surface plasmon polariton scattering by one-dimensional defects of metal surface impedance at oblique incidence. Surface impedance boundary conditions are used to formulate an integral equation which can be solved both analytically and numerically to yield the transmission, reflection, and out-of-plane cross section as a function of angle of incidence and other parameters. Numerical calculations, as well as analytical expressions, obtained within the Born approximation are presented. Green’s tensor approach is also applied so as to expand such analysis to region in which the surface impedance boundary conditions are not appropriate. We show that the angular dependencies for surface plasmon polariton scattering by impedance defects and by surface relief defects are essentially different. The angular dependency of surface plasmon polariton scattering by an impedance defect features an analog to Brewster’s angle that is explained in terms of dipole polarization of the defect.

  10. Texture-dependent anaerobic microsites constrain soil carbon oxidation rates

    NASA Astrophysics Data System (ADS)

    Keiluweit, Marco; Fendorf, Scott

    2016-04-01

    Soil texture, which is a product of parent material, climate and other soil forming factors, is a predictor for long-term storage of soil organic carbon (SOC) storage in many soil ecosystems. Positive correlation between texture (particularly clay content) and SOC storage have long been attributed to protective associations between clay minerals and organic compounds that prevent microbial and enzymatic access - a mechanism commonly referred to as 'mineral protection'. Texture therefore acts as the primary proxy for mineral protection in terrestrial ecosystem models used to assess SOC storage and its sensitivity to global change impacts. Here we show that this protective effect of texture is not only due to mineral protection, but also to the formation of anaerobic microsites. Combining micro-scale laboratory experiments with field-scale observations, we find that oxygen diffusion limitations within clay-rich domains create anaerobic microsites within seemingly well-aerated soils, shifting microbial metabolism to less efficient anaerobic SOC oxidation pathways. Kinetic and thermodynamic constraints reduce SOC oxidation rates within these anaerobic microsites by an order of magnitude relative to aerobic rates, and caused the preservation of bioavailable, polymeric and reduced organic compounds. Lifting these metabolic constraints through increased soil aeration (e.g., through changes in precipitation patterns or land use) may stimulate microbial oxidation of this inherently bioavailable SOC pool. Models that attribute the effects of texture merely to 'mineral protection' may therefore underestimate the vulnerability of soil C to global change impacts.

  11. Histidine oxidation photosensitized by pterin: pH dependent mechanism.

    PubMed

    Castaño, Carolina; Oliveros, Esther; Thomas, Andrés H; Lorente, Carolina

    2015-12-01

    Aromatic pterins accumulate in the skin of patients suffering from vitiligo, a chronic depigmentation disorder, due to the oxidation of tetrahydrobiopterin, the biologically active form of pterins. In this work, we have investigated the ability of pterin, the parent compound of aromatic pterins, to photosensitize the oxidation of histidine in aqueous solutions under UV-A irradiation. Histidine is an α-amino acid with an imidazole functional group, and is frequently present at the active sites of enzymes. The results highlight the role of the pH in controlling the competition between energy and electron transfer mechanisms. It has been previously demonstrated that pterins participate as sensitizers in photosensitized oxidations, both by type I (electron-transfer) and type II mechanisms (singlet oxygen ((1)O2)). By combining different analytical techniques, we could establish that a type I photooxidation was the prevailing mechanism at acidic pH, although a type II mechanism is also present, but it is more important in alkaline solutions.

  12. Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects.

    PubMed

    Drees, Markus; Strassner, Thomas

    2006-03-03

    The oxidation of C-H and C-C bonds by metal-oxo compounds is of general interest. We studied the RuO4-mediated catalytic oxidation of several cycloalkanes such as adamantane and cis- and trans-decalin as well as methane. B3LYP/6-31G(d) calculations on the experimentally proposed (3+2) mechanism are in good agreement with known experimental results. Comparison of experimental and theoretical kinetic isotope effects confirms the proposed mechanism. Besides RuO4, we also looked at RuO4(OH)- as a potential active species to account for ruthenium tetraoxide oxidations under strong basic conditions.

  13. Size- and composition-dependent radio frequency magnetic permeability of iron oxide nanocrystals.

    PubMed

    Yun, Hongseok; Liu, Xiyu; Paik, Taejong; Palanisamy, Duraivelan; Kim, Jungkwun; Vogel, William D; Viescas, Arthur J; Chen, Jun; Papaefthymiou, Georgia C; Kikkawa, James M; Allen, Mark G; Murray, Christopher B

    2014-12-23

    We investigate the size- and composition-dependent ac magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency (RF) applications. The nanocrystals are obtained through high-temperature decomposition synthesis, and their stoichiometry is determined by Mössbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals. All nanocrystalline samples are confirmed to be in the superparamagnetic state at room temperature by SQUID magnetometry. Through the one-turn inductor method, the ac magnetic properties of the nanocrystalline oxides are characterized. In magnetite-rich iron oxide nanocrystals, size-dependent magnetic permeability is not observed, while maghemite iron oxide nanocrystals show clear size dependence. The inductance, resistance, and quality factor of hand-wound inductors with a superparamagnetic composite core are measured. The superparamagnetic nanocrystals are successfully embedded into hand-wound inductors to function as inductor cores.

  14. Size- and Composition-Dependent Radio Frequency Magnetic Permeability of Iron Oxide Nanocrystals

    SciTech Connect

    Yun, H; Liu, XY; Paik, T; Palanisamy, D; Kim, J; Vogel, WD; Viescas, AJ; Chen, J; Papaefthymiou, GC; Kikkawa, JM; Allen, MG; Murray, CB

    2014-12-01

    We investigate the size- and composition-dependent ac magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency (RF) applications. The nanocrystals are obtained through high-temperature decomposition synthesis, and their stoichiometry is determined by Mossbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals. All nanocrystalline samples are confirmed to be in the superparamagnetic state at room temperature by SQUID magnetometry. Through the one-turn inductor method, the ac magnetic properties of the nanocrystalline oxides are characterized. In magnetite-rich iron oxide nanocrystals, size-dependent magnetic permeability is not observed, while maghemite iron oxide nanocrystals show clear size dependence. The inductance, resistance, and quality factor of hand-wound inductors with a superparamagnetic composite core are measured. The superparamagnetic nanocrystals are successfully embedded into hand-wound inductors to function as inductor cores.

  15. Inhibition of vitamin B12-dependent microbial growth by nitrous oxide

    SciTech Connect

    Alston, T.A. )

    1991-01-01

    In methionine-free media, nitrous oxide inhibits the growth of an auxotrophic strain of Escherichia coli lacking a cobalamin-independent pathway for the de novo synthesis of methionine. Prototrophic E. coli is similarly inhibited by nitrous oxide if the cobalamin-independent pathway is selectively depressed by sulfanilamide. Nitrous oxide thus effectively inactivates cobalamin-dependent 5-methyltetrahydrofolate-homocysteine methyltransferase in intact bacteria.

  16. Entrance Channel Mass Asymmetry Effects in Sub-Barrier Fusion Dynamics by Using Energy Dependent Woods-Saxon Potential

    NASA Astrophysics Data System (ADS)

    Manjeet Singh, Gautam

    2015-12-01

    The present article highlights the inconsistency of static Woods-Saxon potential and the applicability of energy dependent Woods-Saxon potential to explore the fusion dynamics of {}4822Ti+58,60,6428Ni, {}4622Ti+{}6428Ni,{}5022Ti+{}6028Ni, and {}199F+9341Nb reactions leading to formation of different Sn-isotopes via different entrance channels. Theoretical calculations based upon one-dimensional Wong formula obtained by using static Woods-Saxon potential unable to provide proper explanation for sub-barrier fusion enhancement of these projectile-target combinations. However, the predictions of one-dimensional Wong formula based upon energy dependent Woods-Saxon potential model (EDWSP model) accurately describe the observed fusion dynamics of these systems wherein the significantly larger value of diffuseness parameter ranging from a = 0.85 fm to a = 0.97 fm is required to address the experimental data in whole range of energy. Therefore, the energy dependence in nucleus-nucleus potential simulates the influence of the nuclear structure degrees of freedom of the colliding pairs. Supported by Dr. D.S. Kothari Post-Doctoral Fellowship Scheme sponsored by University Grants Commission (UGC), New Delhi, India

  17. Blood-Brain Barrier Disruption Caused by Ultrasound Bursts Combined with Microbubbles Depends on Anesthesia

    NASA Astrophysics Data System (ADS)

    McDannold, Nathan; Zhang, Yongzhi; Vykhodtseva, Natalia

    2011-09-01

    Prior works on BBB disruption via inter-arterial infusions of osmotic agents have shown a strong dependence on anesthesia. Here, we investigated whether different anesthesia agents can affect ultrasound-induced BBB disruption. A piston transducer fired through a rubber aperture (frequency: 532 kHz, diameter: 4 cm, aperture diameter: 16 mm) was used to generate the ultrasound fields, and sonications combined with an ultrasound contrast agent were performed at 5 power levels. BBB disruption was quantified by measuring the MRI contrast enhancement in T1-weighted MRI, and erythrocyte extravasation characterized in light microscopy. For each exposure level tested, experiments performed with ketamine/xylazine resulted in significantly greater (P<0.05) enhancement than with isoflurane/oxygen. The onset of severe red blood cell extravasation occurred at lower power levels with ketamine/xylazine. These results suggest ultrasound-induced BBB disruption can depend on anesthesia agent, possibly due effects on the vasculature. These results suggest that care is needed in comparing experiments with different anesthesia agents and physiological factors need to be considered with ultrasound-induced BBB disruption.

  18. Effects of the nitric oxide donor JS-K on the blood-tumor barrier and on orthotopic U87 rat gliomas assessed by MRI.

    PubMed

    Weidensteiner, Claudia; Reichardt, Wilfried; Shami, Paul J; Saavedra, Joseph E; Keefer, Larry K; Baumer, Brunhilde; Werres, Anna; Jasinski, Robert; Osterberg, Nadja; Weyerbrock, Astrid

    2013-04-01

    Nitric oxide (NO) released from NO donors can be cytotoxic in tumor cells and can enhance the transport of drugs into brain tumors by altering blood-tumor barrier permeability. The NO donor JS-K [O(2)-(2,4-dinitrophenyl) 1-[(4-ethoxycarbonyl)piperazin-1-yl]diazen-1-ium-1,2-diolate] releases NO upon enzymatic activation selectively in cells overexpressing glutathione-S-transferases (GSTs) such as gliomas. Thus, JS-K-dependent NO effects - especially on cell viability and vascular permeability - were investigated in U87 glioma cells in vitro and in an orthotopic U87 xenograft model in vivo by magnetic resonance imaging (MRI). In vitro experiments showed dose-dependent antiproliferative and cytotoxic effects in U87 cells. In addition, treatment of U87 cells with JS-K resulted in a dose-dependent activation of soluble guanylate cyclase and intracellular accumulation of cyclic guanosine monophosphate (cGMP) which was irreversibly inhibited by the selective inhibitor of soluble guanylate cyclase ODQ (1H-[1,2,4]oxadiazolo(4,3a)quinoxaline-1-one). Using dynamic contrast enhanced MRI (DCE-MRI) as a minimally invasive technique, we demonstrated for the first time a significant increase in the DCE-MRI read-out initial area under the concentration curve (iAUC60) indicating an acute increase in blood-tumor barrier permeability after i.v. treatment with JS-K. Repeated MR imaging of animals with intracranial U87 gliomas under treatment with JS-K (3.5 μmol/kg JS-K 3×/week) and of untreated controls on day 12 and 19 after tumor inoculation revealed no significant changes in tumor growth, edema formation or tumor perfusion. Immunohistochemical workup of the brains showed a significant antiproliferative effect of JS-K in the gliomas. Taken together, in vitro and in vivo data suggest that JS-K has antiproliferative effects in U87 gliomas and opens the blood-tumor barrier by activation of the NO/cGMP signaling pathway. This might be a novel approach to facilitate entry of therapeutic

  19. Huntingtin inclusion bodies are iron-dependent centers of oxidative events.

    PubMed

    Firdaus, Wance J J; Wyttenbach, Andreas; Giuliano, Paola; Kretz-Remy, Carole; Currie, R William; Arrigo, André-Patrick

    2006-12-01

    Recently, we reported that the transient expression of huntingtin exon1 polypeptide containing polyglutamine tracts of various sizes (httEx1-polyQ) in cell models of Huntington disease generated an oxidative stress whose intensity was CAG repeat expansion-dependent. Here, we have analyzed the intracellular localization of the oxidative events generated by the httEx1-polyQ polypeptides. Analysis of live COS-7 cells as well as neuronal SK-N-SH and PC12 cells incubated with hydroethidine or dichlorofluorescein diacetate revealed oxidation of these probes at the level of the inclusion bodies formed by httEx1-polyQ polypeptides. The intensity and frequency of the oxidative events among the inclusions were CAG repeat expansion-dependent. Electron microscopic analysis of cell sections revealed the presence of oxidation-dependent morphologic alterations in the vicinity of httEx1-polyQ inclusion bodies. Moreover, a high level of oxidized proteins was recovered in partially purified inclusions. We also report that the iron chelator deferroxamine altered the structure, localization and oxidative potential of httEx1-polyQ inclusion bodies. Hence, despite the fact that the formation of inclusion bodies may represent a defense reaction of the cell to eliminate httEx1 mutant polypeptide, this phenomenon appears inherent to the generation of iron-dependent oxidative events that can be deleterious to the cell.

  20. Improved free energy profile for reduction of NO in cytochrome c dependent nitric oxide reductase (cNOR).

    PubMed

    Blomberg, Margareta R A; Siegbahn, Per E M

    2016-07-15

    Quantum chemical calculations play an essential role in the elucidation of reaction mechanisms for redox-active metalloenzymes. For example, the cleavage and the formation of covalent bonds can usually not be described only on the basis of experimental information, but can be followed by the calculations. Conversely, there are properties, like reduction potentials, which cannot be accurately calculated. Therefore, computational and experimental data has to be carefully combined to obtain reliable descriptions of entire catalytic cycles involving electron and proton uptake from donors outside the enzyme. Such a procedure is illustrated here, for the reduction of nitric oxide (NO) to nitrous oxide and water in the membrane enzyme, cytochrome c dependent nitric oxide reductase (cNOR). A surprising experimental observation is that this reaction is nonelectrogenic, which means that no energy is conserved. On the basis of hybrid density functional calculations a free energy profile for the entire catalytic cycle is obtained, which agrees much better with experimental information on the active site reduction potentials than previous ones. Most importantly the energy profile shows that the reduction steps are endergonic and that the entire process is rate-limited by high proton uptake barriers during the reduction steps. This result implies that, if the reaction were electrogenic, it would become too slow when the gradient is present across the membrane. This explains why this enzyme does not conserve any of the free energy released. © 2016 Wiley Periodicals, Inc.

  1. LOXL2 Oxidizes Methylated TAF10 and Controls TFIID-Dependent Genes during Neural Progenitor Differentiation.

    PubMed

    Iturbide, Ane; Pascual-Reguant, Laura; Fargas, Laura; Cebrià, Joan Pau; Alsina, Berta; García de Herreros, Antonio; Peiró, Sandra

    2015-06-04

    Protein function is often regulated and controlled by posttranslational modifications, such as oxidation. Although oxidation has been mainly considered to be uncontrolled and nonenzymatic, many enzymatic oxidations occur on enzyme-selected lysine residues; for instance, LOXL2 oxidizes lysines by converting the ε-amino groups into aldehyde groups. Using an unbiased proteomic approach, we have identified methylated TAF10, a member of the TFIID complex, as a LOXL2 substrate. LOXL2 oxidation of TAF10 induces its release from its promoters, leading to a block in TFIID-dependent gene transcription. In embryonic stem cells, this results in the inactivation of the pluripotency genes and loss of the pluripotent capacity. During zebrafish development, the absence of LOXL2 resulted in the aberrant overexpression of the neural progenitor gene Sox2 and impaired neural differentiation. Thus, lysine oxidation of the transcription factor TAF10 is a controlled protein modification and demonstrates a role for protein oxidation in regulating pluripotency genes.

  2. Size Dependence of [n]Cycloparaphenylenes (n=5-12) in Electrochemical Oxidation.

    PubMed

    Kayahara, Eiichi; Fukayama, Kei; Nishinaga, Tohru; Yamago, Shigeru

    2016-06-21

    The oxidation processes of [n]cycloparaphenylenes ([n]CPPs) (n=5-12) were systematically investigated by cyclic and rotating disk electrode voltammetry. All CPPs underwent pseudo-reversible two-electron oxidation irrespective of ring size, forming the corresponding radical cations and then dications. The results were in sharp contrast to those observed for linear oligoparaphenylenes, which only undergo one-electron oxidation. The difference in the first and second oxidation potentials in the CPP oxidation was affected by the ring size and became more significant as the decrease of CPP size. In other words, while the first oxidation from neutral CPP to the radical cation occurred faster as the size of CPP becomes smaller, the second oxidation from the radical cation to dication exhibited opposite size dependence.

  3. Boswellia serrata Preserves Intestinal Epithelial Barrier from Oxidative and Inflammatory Damage.

    PubMed

    Catanzaro, Daniela; Rancan, Serena; Orso, Genny; Dall'Acqua, Stefano; Brun, Paola; Giron, Maria Cecilia; Carrara, Maria; Castagliuolo, Ignazio; Ragazzi, Eugenio; Caparrotta, Laura; Montopoli, Monica

    2015-01-01

    Aminosalicylates, corticosteroids and immunosuppressants are currently the therapeutic choices in inflammatory bowel diseases (IBD), however, with limited remission and often serious side effects. Meanwhile complementary and alternative medicine (CAM) use is increasing, particularly herbal medicine. Boswellia serrata is a traditional Ayurvedic remedy with anti-inflammatory properties, of interest for its usefulness in IBDs. The mechanism of this pharmacological potential of Boswellia serrata was investigated in colonic epithelial cell monolayers exposed to H2O2 or INF-γ+TNF-α, chosen as in vitro experimental model of intestinal inflammation. The barrier function was evaluated by the transepithelial electrical resistance (TEER) and paracellular permeability assay, and by the tight junction proteins (zonula occludens-1, ZO-1 and occludin) immunofluorescence. The expression of phosphorylated NF-κB and reactive oxygen species (ROS) generation were determined by immunoblot and cytofluorimetric assay, respectively. Boswellia serrata oleo-gum extract (BSE) and its pure derivative acetyl-11-keto-β-boswellic acid (AKBA), were tested at 0.1-10 μg/ml and 0.027 μg/ml, respectively. BSE and AKBA safety was demonstrated by no alteration of intestinal cell viability and barrier function and integrity biomarkers. H2O2 or INF-γ+TNF-α treatment of Caco-2 cell monolayers significantly reduced TEER, increased paracellular permeability and caused the disassembly of tight junction proteins occludin and ZO-1. BSE and AKBA pretreatment significantly prevented functional and morphological alterations and also the NF-κB phosphorylation induced by the inflammatory stimuli. At the same concentrations BSE and AKBA counteracted the increase of ROS caused by H2O2 exposure. Data showed the positive correlation of the antioxidant activity with the mechanism involved in the physiologic maintenance of the integrity and function of the intestinal epithelium. This study elucidates the

  4. Boswellia serrata Preserves Intestinal Epithelial Barrier from Oxidative and Inflammatory Damage

    PubMed Central

    Catanzaro, Daniela; Rancan, Serena; Orso, Genny; Dall’Acqua, Stefano; Brun, Paola; Giron, Maria Cecilia; Carrara, Maria; Castagliuolo, Ignazio; Ragazzi, Eugenio; Caparrotta, Laura; Montopoli, Monica

    2015-01-01

    Aminosalicylates, corticosteroids and immunosuppressants are currently the therapeutic choices in inflammatory bowel diseases (IBD), however, with limited remission and often serious side effects. Meanwhile complementary and alternative medicine (CAM) use is increasing, particularly herbal medicine. Boswellia serrata is a traditional Ayurvedic remedy with anti-inflammatory properties, of interest for its usefulness in IBDs. The mechanism of this pharmacological potential of Boswellia serrata was investigated in colonic epithelial cell monolayers exposed to H2O2 or INF-γ+TNF-α, chosen as in vitro experimental model of intestinal inflammation. The barrier function was evaluated by the transepithelial electrical resistance (TEER) and paracellular permeability assay, and by the tight junction proteins (zonula occludens-1, ZO-1 and occludin) immunofluorescence. The expression of phosphorylated NF-κB and reactive oxygen species (ROS) generation were determined by immunoblot and cytofluorimetric assay, respectively. Boswellia serrata oleo-gum extract (BSE) and its pure derivative acetyl-11-keto-β-boswellic acid (AKBA), were tested at 0.1-10 μg/ml and 0.027μg/ml, respectively. BSE and AKBA safety was demonstrated by no alteration of intestinal cell viability and barrier function and integrity biomarkers. H2O2 or INF-γ+TNF-α treatment of Caco-2 cell monolayers significantly reduced TEER, increased paracellular permeability and caused the disassembly of tight junction proteins occludin and ZO-1. BSE and AKBA pretreatment significantly prevented functional and morphological alterations and also the NF-κB phosphorylation induced by the inflammatory stimuli. At the same concentrations BSE and AKBA counteracted the increase of ROS caused by H2O2 exposure. Data showed the positive correlation of the antioxidant activity with the mechanism involved in the physiologic maintenance of the integrity and function of the intestinal epithelium. This study elucidates the

  5. Interfacing BiVO4 with Reduced Graphene Oxide for Enhanced Photoactivity: A Tale of Facet Dependence of Electron Shuttling.

    PubMed

    Tan, Hui Ling; Tahini, Hassan A; Wen, Xiaoming; Wong, Roong Jien; Tan, Xin; Iwase, Akihide; Kudo, Akihiko; Amal, Rose; Smith, Sean C; Ng, Yun Hau

    2016-10-01

    Efficient interfacial charge transfer is essential in graphene-based semiconductors to realize their superior photoactivity. However, little is known about the factors (for example, semiconductor morphology) governing the charge interaction. Here, it is demonstrated that the electron transfer efficacy in reduced graphene oxide-bismuth oxide (RGO/BiVO4 ) composite is improved as the relative exposure extent of {010}/{110} facets on BiVO4 increases, indicated by the greater extent of photocurrent enhancement. The dependence of charge transfer ability on the exposure degree of {010} relative to {110} is revealed to arise due to the difference in electronic structures of the graphene/BiVO4 {010} and graphene/BiVO4 {110} interfaces, as evidenced by the density functional theory calculations. The former interface is found to be metallic with higher binding energy and smaller Schottky barrier than that of the latter semiconducting interface. The facet-dependent charge interaction elucidated in this study provides new aspect for design of graphene-based semiconductor photocatalyst useful in manifold applications.

  6. Development of oxide based diffusion barrier coatings for CFC components applied in modern furnaces

    NASA Astrophysics Data System (ADS)

    Bobzin, Kirsten; Zhao, Lidong; Schlaefer, Thomas; Warda, Thomas

    2011-12-01

    Carbon fibre reinforced carbon (CFC) materials show a high potential for usage in furnaces as sample carriers for example, which is due to their excellent thermal stability compared to steel carriers. Only their tendency to react with different metals at high temperatures by Cdiffusion is a disadvantage, which can be solved by application of diffusion barriers. In order to enable the utilization of CFC-carriers for e.g. brazing furnaces, within the frame of this study thermally sprayed diffusion barrier coatings were developed. Coatings of mullite and ZrO2-7% Y2O3 (YSZ) were prepared by air plasma spraying (APS). The coatings were investigated in terms of their microstructure and thermal shock behaviour. In order to prove the suitability of the coatings for the application in brazing furnaces, the wettability of the coating surfaces by a Ni-based brazing alloy was investigated. The results showed that both mullite and YSZ could be deposited on CFC substrates with a bond coat of W or SiC. Both coatings exhibited good thermal shock behaviour and an excellent non-wetting behaviour against the used Ni-based braze alloy.

  7. Magnetic resonance imaging of post-ischemic blood-brain barrier damage with PEGylated iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Dong-Fang; Qian, Cheng; An, Yan-Li; Chang, Di; Ju, Sheng-Hong; Teng, Gao-Jun

    2014-11-01

    Blood-brain barrier (BBB) damage during ischemia may induce devastating consequences like cerebral edema and hemorrhagic transformation. This study presents a novel strategy for dynamically imaging of BBB damage with PEGylated supermagnetic iron oxide nanoparticles (SPIONs) as contrast agents. The employment of SPIONs as contrast agents made it possible to dynamically image the BBB permeability alterations and ischemic lesions simultaneously with T2-weighted MRI, and the monitoring could last up to 24 h with a single administration of PEGylated SPIONs in vivo. The ability of the PEGylated SPIONs to highlight BBB damage by MRI was demonstrated by the colocalization of PEGylated SPIONs with Gd-DTPA after intravenous injection of SPION-PEG/Gd-DTPA into a mouse. The immunohistochemical staining also confirmed the leakage of SPION-PEG from cerebral vessels into parenchyma. This study provides a novel and convenient route for imaging BBB alteration in the experimental ischemic stroke model.

  8. Nitric oxide-dependent posttranslational modification in plants: an update.

    PubMed

    Astier, Jeremy; Lindermayr, Christian

    2012-11-16

    Nitric oxide (NO) has been demonstrated as an essential regulator of several physiological processes in plants. The understanding of the molecular mechanism underlying its critical role constitutes a major field of research. NO can exert its biological function through different ways, such as the modulation of gene expression, the mobilization of second messengers, or interplays with protein kinases. Besides this signaling events, NO can be responsible of the posttranslational modifications (PTM) of target proteins. Several modifications have been identified so far, whereas metal nitrosylation, the tyrosine nitration and the S-nitrosylation can be considered as the main ones. Recent data demonstrate that these PTM are involved in the control of a wide range of physiological processes in plants, such as the plant immune system. However, a great deal of effort is still necessary to pinpoint the role of each PTM in plant physiology. Taken together, these new advances in proteomic research provide a better comprehension of the role of NO in plant signaling.

  9. Kinetic-dependent Killing of Oral Pathogens with Nitric Oxide

    PubMed Central

    Backlund, C.J.; Worley, B.V.; Sergesketter, A.R.

    2015-01-01

    Nitric oxide (NO)–releasing silica nanoparticles were synthesized via the co-condensation of tetramethyl orthosilicate with aminosilanes and subsequent conversion of secondary amines to N-diazeniumdiolate NO donors. A series of ~150 nm NO-releasing particles with different NO totals and release kinetics (i.e., half-lives) were achieved by altering both the identity and mol% composition of the aminosilane precursors. Independent of identical 2 h NO-release totals, enhanced antibacterial action was observed against the periodontopathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis with extended NO-release kinetics at pH 7.4. Negligible bactericidal effect was observed against cariogenic Streptococcus mutans at pH 7.4, even when using NO-releasing silica particles with greater NO-release totals. However, antibacterial activity was observed against S. mutans at lower pH (6.4). This result was attributed to more rapid proton-initiated decomposition of the N-diazeniumdiolate NO donors and greater NO-release payloads. The data suggest a differential sensitivity to NO between cariogenic and periodontopathogenic bacteria with implications for the future development of NO-releasing oral care therapeutics. PMID:26078424

  10. Nitric Oxide-Dependent Posttranslational Modification in Plants: An Update

    PubMed Central

    Astier, Jeremy; Lindermayr, Christian

    2012-01-01

    Nitric oxide (NO) has been demonstrated as an essential regulator of several physiological processes in plants. The understanding of the molecular mechanism underlying its critical role constitutes a major field of research. NO can exert its biological function through different ways, such as the modulation of gene expression, the mobilization of second messengers, or interplays with protein kinases. Besides this signaling events, NO can be responsible of the posttranslational modifications (PTM) of target proteins. Several modifications have been identified so far, whereas metal nitrosylation, the tyrosine nitration and the S-nitrosylation can be considered as the main ones. Recent data demonstrate that these PTM are involved in the control of a wide range of physiological processes in plants, such as the plant immune system. However, a great deal of effort is still necessary to pinpoint the role of each PTM in plant physiology. Taken together, these new advances in proteomic research provide a better comprehension of the role of NO in plant signaling. PMID:23203119

  11. Temperature dependent rheological property of copper oxide nanoparticles suspension (nanofluid).

    PubMed

    Kulkarni, Devdatta P; Das, Debendra K; Chukwu, Godwin A

    2006-04-01

    A nanofluid is the dispersion of metallic solid particles of nanometer size in a base fluid such as water or ethylene glycol. The presence of these nanoparticles affects the physical properties of a nanofluid via various factors including shear stress, particle loading, and temperature. In this paper the rheological behavior of copper oxide (CuO) nanoparticles of 29 nm average diameter dispersed in deionized (DI) water is investigated over a range of volumetric solids concentrations of 5 to 15% and various temperatures varying from 278-323 degrees K. These experiments showed that these nanofluids exhibited time-independent pseudoplastic and shear-thinning behavior. The suspension viscosities of nanofluids decrease exponentially with respect to the shear rate. Suspension viscosity follows the correlation in the form ln(mus) = A(1/T)-B, where constants A and B are the functions of volumetric concentrations. The calculated viscosities from the developed correlations and experimental values were found to be within +/- 10% of their values.

  12. Ultraviolet-oxidized mercaptan-terminated organosilane nanolayers as diffusion barriers at Cu-silica interfaces

    NASA Astrophysics Data System (ADS)

    Gandhi, D. D.; Tisch, U.; Singh, B.; Eizenberg, M.; Ramanath, G.

    2007-10-01

    We demonstrate the use of UV-exposed molecular nanolayers (MNLs) of 3-mercaptan-propyl-trimethoxysilane to inhibit copper-transport across Cu -SiO2 interfaces more efficiently than the pristine MNLs. Bias-thermal-annealing tests of Cu /MNL/SiO2/Si(001)/Al capacitors, with MNLs exposed to 254nm UV radiation, exhibit enhanced barrier properties to Cu diffusion, when compared with capacitors with MNLs not exposed to UV light. X-ray photoelectron spectroscopy reveals that UV exposure converts the mercaptan termini to sulfonates, which are more effective in inhibiting Cu diffusion. Our findings are of importance for tailoring the chemical and mechanical integrity of interfaces for use in applications such as nanodevice wiring and molecular electronics.

  13. DEPENDENCE OF NITRIC OXIDE EMISSIONS ON VEHICLE LOAD: RESULTS FROM THE GTRP INSTRUMENTED VEHICLE PROGRAM

    EPA Science Inventory

    The presentation discussed the dependence of nitric oxide (NO) emissions on vehicle load, bases on results from an instrumented-vehicle program. The accuracy and feasibility of modal emissions models depend on algorithms to allocate vehicle emissions based on a vehicle operation...

  14. Nitric oxide mediates local activity-dependent excitatory synapse development.

    PubMed

    Nikonenko, Irina; Nikonenko, Alexander; Mendez, Pablo; Michurina, Tatyana V; Enikolopov, Grigori; Muller, Dominique

    2013-10-29

    Learning related paradigms play an important role in shaping the development and specificity of synaptic networks, notably by regulating mechanisms of spine growth and pruning. The molecular events underlying these synaptic rearrangements remain poorly understood. Here we identify NO signaling as a key mediator of activity-dependent excitatory synapse development. We find that chronic blockade of NO production in vitro and in vivo interferes with the development of hippocampal and cortical excitatory spine synapses. The effect results from a selective loss of activity-mediated spine growth mechanisms and is associated with morphological and functional alterations of remaining synapses. These effects of NO are mediated by a cGMP cascade and can be reproduced or prevented by postsynaptic expression of vasodilator-stimulated phosphoprotein phospho-mimetic or phospho-resistant mutants. In vivo analyses show that absence of NO prevents the increase in excitatory synapse density induced by environmental enrichment and interferes with the formation of local clusters of excitatory synapses. We conclude that NO plays an important role in regulating the development of excitatory synapses by promoting local activity-dependent spine-growth mechanisms.

  15. Covalent dependence of octahedral rotations in orthorhombic perovskite oxides.

    PubMed

    Cammarata, Antonio; Rondinelli, James M

    2014-09-21

    The compositional dependence of metal-oxygen BO6 octahedral distortions, including bond elongations and rotations, is frequently discussed in the ABO3 perovskite literature; structural distortions alleviate internal stresses driven by under- or over-coordinated bond environments. Here we identify the dependence of octahedral rotations from changes in metal-oxygen bond covalency in orthorhombic perovskites. Using density functional theory we formulate a covalency metric, which captures both the real and k-space interactions between the magnitude and sense, i.e., in-phase or out-of-phase, octahedral rotations, to explore the link between the ionic-covalent Fe-O bond and the interoctahedral Fe-O-Fe bond angles in Pbnm ferrates. Our survey finds that the covalency of the metal-oxygen bond is correlated with the rotation amplitude: We find the more covalent the Fe-O bond, the less distorted is the structure and the more important the long-range inter-octahedral (Fe-O-Fe bond angle) interactions. Finally, we show how to indirectly tune the B-O bond covalency by A-cation induced BO6 rotations independent of ionic size, facilitating design of targeted bonding interactions in complex perovskites.

  16. pH-dependent growth of zinc oxide nanorods

    NASA Astrophysics Data System (ADS)

    Baruah, Sunandan; Dutta, Joydeep

    2009-04-01

    Here we study the effect of pH variation on the dimension and morphology of zinc oxide (ZnO) nanorods grown through hydrothermal process at temperatures less than 100 °C. ZnO nanorods were grown on pre-seeded glass substrates using zinc nitrate hexahydrate as the source of Zn ions and hexamethylenetetramine as the source of hydroxyl ions. The pH of the reaction bath was found to change gradually from 6.4 to 7.3 in 5 h during the growth process. The growth of the ZnO nanorods was observed to be faster, both laterally and longitudinally, when the growth solution was in basic conditions. However, flower petal like ZnO nanostructures were obtained when the growth process was initiated in basic condition (pH 8-12), indicating that initial acidic conditions were required to obtain nanorods with well-defined hexagonal facets. ZnO is known to erode in acidic condition and the final dimension of the nanorods is determined by a competition between crystal growth and etching. ZnO nanorods of different dimensions, both laterally (diameters ranging from 220 nm to 1 μm) and longitudinally (lengths ranging from 1 to 5.6 μm) were successfully synthesized using the same concentration of zinc nitrate and hexamine in the reaction bath and the same growth duration of 5 h simply through appropriate control of the pH of the reactant solution between 6 and 7.3.

  17. A graphene-oxide-based thin coating on the separator: an efficient barrier towards high-stable lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Yunbo; Miao, Lixiao; Ning, Jing; Xiao, Zhichang; Hao, Long; Wang, Bin; Zhi, Linjie

    2015-06-01

    The electrochemical performance of lithium-sulfur (Li-S) batteries can be significantly improved by simply coating a thin barrier layer on the separator. The spray-coating of a mixture of graphene oxides (GO) and oxidized carbon nanotubes (o-CNT) can achieve a barrier coating of only 0.3 mg cm-2, which is much less than conventional interlayers and has no negative impact on the energy density but significantly enhances the electrochemical performances of the whole battery device. Due to the binding forces induced by functional groups on GO and the interconnected nanoscale channels provided by o-CNT, the thus fabricated Li-S batteries show dramatically improved specific discharge capacities of up to 750 mAh g-1 at 1 C even after 100 cycles, more than twice those of batteries without barrier coatings.

  18. Application of Iron Oxide as a pH-dependent Indicator for Improving the Nutritional Quality

    PubMed Central

    2016-01-01

    Acid food indicators can be used as pH indicators for evaluating the quality and freshness of fermented products during the full course of distribution. Iron oxide particles are hardly suspended in water, but partially or completely agglomerated. The agglomeration degree of the iron oxide particles depends on the pH. The pH-dependent particle agglomeration or dispersion can be useful for monitoring the acidity of food. The zeta potential of iron oxide showed a decreasing trend as the pH increased from 2 to 8, while the point of zero charge (PZC) was observed around at pH 6.0-7.0. These results suggested that the size of the iron oxide particles was affected by the change in pH levels. As a result, the particle sizes of iron oxide were smaller at lower pH than at neutral pH. In addition, agglomeration of the iron oxide particles increased as the pH increased from 2 to 7. In the time-dependent aggregation test, the average particle size was 730.4 nm and 1,340.3 nm at pH 2 and 7, respectively. These properties of iron oxide particles can be used to develop an ideal acid indicator for food pH and to monitor food quality, besides a colorant or nutrient for nutrition enhancement and sensory promotion in food industry. PMID:27482521

  19. Influence of capillary barrier effect on biogas distribution at the base of passive methane oxidation biosystems: Parametric study.

    PubMed

    Ahoughalandari, Bahar; Cabral, Alexandre R

    2016-12-05

    The efficiency of methane oxidation in passive methane oxidation biosystems (PMOBs) is influenced by, among other things, the intensity and distribution of the CH4 loading at the base of the methane oxidation layer (MOL). Both the intensity and distribution are affected by the capillary barrier that results from the superposition of the two materials constituting the PMOB, namely the MOL and the gas distribution layer (GDL). The effect of capillary barriers on the unsaturated flow of water has been well documented in the literature. However, its effect on gas flow through PMOBs is still poorly documented. In this study, sets of numerical simulations were performed to evaluate the effect of unsaturated hydraulic characteristics of the MOL material on the value and distribution of moisture and hence, the ease and uniformity in the distribution of the upward flow of biogas along the GDL-MOL interface. The unsaturated hydraulic parameters of the materials used to construct the experimental field plot at the St-Nicephore landfill (Quebec, Canada) were adopted to build the reference simulation of the parametric study. The behavior of the upward flow of biogas for this particular material was analyzed based on its gas intrinsic permeability function, which was obtained in the laboratory. The parameters that most influenced the distribution and the ease of biogas flow at the base of the MOL were the saturated hydraulic conductivity and pore size distribution of the MOL material, whose effects were intensified as the slope of the interface increased. The effect of initial dry density was also assessed herein. Selection of the MOL material must be made bearing in mind that these three parameters are key in the effort to prevent unwanted restriction in the upward flow of biogas, which may result in the redirection of biogas towards the top of the slope, leading to high CH4 fluxes (hotspots). In a well-designed PMOB, upward flow of biogas across the GDL-MOL interface is

  20. Cr K-Edge XANES Spectroscopy: Ligand and Oxidation State Dependence — What is Oxidation State?

    NASA Astrophysics Data System (ADS)

    Tromp, Moniek; Moulin, Jerome; Reid, Gillian; Evans, John

    2007-02-01

    A series of Cr complexes varying in oxidation state, ligand and geometry were studied with Cr K-edge XANES. The main absorption edge energy shift for an oxidation state change from Cr0 to Cr6+ is found to be similar to that for a series of Cr3+ complexes with different ligands. Theoretical XANES and density of states calculations using FEFF8.0 provided detailed insights in the origin of the XANES features for the series of distorted octahedral CrCl3L complexes. The geometry of the CrCl3L complex governs the position of the main absorption edge. Hard versus soft donor effects are overruled by the chlorine ligand for complexes with a facial geometry, whereas the chlorine ligand does not play a significant role in meridional geometry. The combined results call for a redefinition of generally used concepts like oxidation state.

  1. Enalapril attenuates ischaemic brain oedema and protects the blood-brain barrier in rats via an anti-oxidant action.

    PubMed

    Panahpour, Hamdollah; Dehghani, Gholam Abbas; Bohlooli, Shahab

    2014-03-01

    1. In the present study, we investigated the effects of postischaemic angiotensin-converting enzyme (ACE) inhibition with enalapril on vasogenic oedema formation and blood-brain barrier (BBB) integrity following transient focal cerebral ischaemia in rats. 2. Cerebral ischaemia was induced by 60 min occlusion of the right middle cerebral artery, followed by 24 h reperfusion. Vehicle and a non-hypotensive dose of enalapril (0.03 mg/kg) were administered at the beginning of the reperfusion period. A neurological deficit score (NDS) was determined for all rats at the end of the reperfusion period. Then, brain oedema formation was investigated using the wet-dry weight method and BBB permeability was evaluated on the basis of extravasation of Evans blue (EB) dye. In addition, oxidative stress was assessed by measuring reduced glutathione (GSH) and malondialdehyde (MDA) in brain homogenates. 3. Inhibition of ACE by enalapril significantly reduced NDS and decreased brain oedema formation (P < 0.05 for both). Disruption of the BBB following ischaemia resulted in considerable leakage of EB dye into the brain parenchyma of the ipsilateral hemispheres of vehicle-treated rats. Enalapril significantly (P < 0.05) decreased EB extravasation into the lesioned hemisphere. Enalapril also augmented anti-oxidant activity in ischaemic brain tissue by increasing GSH concentrations and significantly (P < 0.05) attenuating the increased MDA levels in response to ischaemia. 4. In conclusion, inhibition of ACE with a non-hypotensive dose of enalapril may protect BBB function and attenuate oedema formation via anti-oxidant actions.

  2. Low-Thermal-Conductivity Pyrochlore Oxide Materials Developed for Advanced Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Zhu, Dong-Ming

    2005-01-01

    When turbine engines operate at higher temperatures, they consume less fuel, have higher efficiencies, and have lower emissions. The upper-use temperatures of the base materials (superalloys, silicon-based ceramics, etc.) used for the hot-section components of turbine engines are limited by the physical, mechanical, and corrosion characteristics of these materials. Thermal barrier coatings (TBCs) are applied as thin layers on the surfaces of these materials to further increase the operating temperatures. The current state-of-the-art TBC material in commercial use is partially yttria-stabilized zirconia (YSZ), which is applied on engine components by plasma spraying or by electron-beam physical vapor deposition. At temperatures higher than 1000 C, YSZ layers are prone to sintering, which increases thermal conductivity and makes them less effective. The sintered and densified coatings can also reduce thermal stress and strain tolerance, which can reduce the coating s durability significantly. Alternate TBC materials with lower thermal conductivity and better sintering resistance are needed to further increase the operating temperature of turbine engines.

  3. Failure Morphologies of Cyclically Oxidized ZrO2-Based Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Nesbitt, James A.; Zhu, Dongming; Miller, Robert A.; Barrett, Charles A.

    2002-01-01

    Advanced and baseline thermal barrier coatings (TBCs) were thermal cycle tested in air at 1163 C until delamination or spallation of the ceramic top coat. The top coat of the advanced TBC s consisted of ZrO2 with various amounts of Y2O3, Yb2O3, Gd2O3, or Nd2O3 dopants. The composition of the top coat of the baseline TBC was ZrO2-8wt.%Y2O3. All top coats were deposited by air plasma spraying. A NiCrAlY or NiCoCrAlY bond coat was deposited by low pressure plasma spraying onto a single-crystal, Ni-base superalloy. The TBC lifetime for the baseline coatings was approximately 190 cycles (45 minutes at 1163 C per cycle) while the lifetime for the advanced coatings was as high as 425 cycles. The fracture surfaces and sample cross sections were examined after TBC failure by SEM and optical microscopy, and the top coats were further examined by X-ray diffraction. These post-test studies revealed that the fracture path largely followed splat boundaries with some trans-splat fracture. However, there were no obvious distinguishing features which explained the difference in TBC lifetimes between some of the advanced and baseline coatings.

  4. Phosphorylation of Grainy head by ERK is essential for wound-dependent regeneration but not for development of an epidermal barrier.

    PubMed

    Kim, Myungjin; McGinnis, William

    2011-01-11

    Grainy head (GRH) is a key transcription factor responsible for epidermal barrier formation and repair, whose function is highly conserved across diverse animal species. However, it is not known how GRH function is reactivated to repair differentiated epidermal barriers after wounding. Here, we show that GRH is directly regulated by extracellular signal-regulated kinase (ERK) phosphorylation, which is required for wound-dependent expression of GRH target genes in epidermal cells. Serine 91 is the principal residue in GRH that is phosphorylated by ERK. Although mutations of the ERK phosphorylation sites in GRH do not impair its DNA binding function, the ERK sites in GRH are required to activate Dopa decarboxylase (Ddc) and misshapen (msn) epidermal wound enhancers as well as functional regeneration of an epidermal barrier upon wounding. This result indicates that the phosphorylation sites are essential for damaged epidermal barrier repair. However, GRH with mutant ERK phosphorylation sites can still promote barrier formation during embryonic epidermal development, suggesting that ERK sites are dispensable for the GRH function in establishing epidermal barrier integrity. These results provide mechanistic insight into how tissue repair can be initiated by posttranslational modification of a key transcription factor that normally mediates the developmental generation of that tissue.

  5. Junction-Structure-Dependent Schottky Barrier Inhomogeneity and Device Ideality of Monolayer MoS2 Field-Effect Transistors.

    PubMed

    Moon, Byoung Hee; Han, Gang Hee; Kim, Hyun; Choi, Homin; Bae, Jung Jun; Kim, Jaesu; Jin, Youngjo; Jeong, Hye Yun; Joo, Min-Kyu; Lee, Young Hee; Lim, Seong Chu

    2017-03-29

    Although monolayer transition metal dichalcogenides (TMDs) exhibit superior optical and electrical characteristics, their use in digital switching devices is limited by incomplete understanding of the metal contact. Comparative studies of Au top and edge contacts with monolayer MoS2 reveal a temperature-dependent ideality factor and Schottky barrier height (SBH). The latter originates from inhomogeneities in MoS2 caused by defects, charge puddles, and grain boundaries, which cause local variation in the work function at Au-MoS2 junctions and thus different activation temperatures for thermionic emission. However, the effect of inhomogeneities due to impurities on the SBH varies with the junction structure. The weak Au-MoS2 interaction in the top contact, which yields a higher SBH and ideality factor, is more affected by inhomogeneities than the strong interaction in the edge contact. Observed differences in the SBH and ideality factor in different junction structures clarify how the SBH and inhomogeneities can be controlled in devices containing TMD materials.

  6. The Dependence of the Ultrasound-Induced Blood-Brain Barrier Opening Characteristics on Microbubble Size In Vivo

    NASA Astrophysics Data System (ADS)

    Choi, James J.; Feshitan, Jameel A.; Wang, Shougang; Tung, Yao-Sheng; Baseri, Babak; Borden, Mark A.; Konofagou, Elisa E.

    2009-04-01

    Recent neuropharmaceutical developments have led to potent disease-modifying drugs. In spite of these advancements, most agents cannot traverse the blood-brain barrier (BBB) and deposit in the brain. Focused ultrasound (FUS) with microbubbles has been shown to induce noninvasive, localized, and transient BBB opening. Although promising, safety and efficacy concerns still remain. Previously reported experiments used conventional imaging contrast agents that have a wide size distribution. In this study, we hypothesize that BBB opening characteristics are dependent on bubble diameter. A 25 μl bolus of in-house manufactured, lipid-shelled bubbles with either 1-2 or 4-5 μm diameter ranges was injected intravenously. Pulsed FUS (frequency: 1.5 MHz, peak-negative pressure: 146-607 kPa, duty cycle: 20%, duration: 1-min) was then applied to the left hippocampus of mice (n = 16) in vivo through the intact skin and skull. MRI or fluorescence microscopy was used to determine BBB opening. Contrast-enhanced (Omniscan™; 0.75 mL; molecular weight: 574 Da) MRI (9.4-T) was acquired on multiple days after sonication to determine BBB opening and closing. Fluorescence microscopy was also used to determine the feasibility of delivering large, 3 kDa dextran compounds through the BBB. The BBB opening acoustic pressure threshold for the 4-5μm bubbles was in the 146-304 kPa range while the threshold for the 1-2μm bubbles was higher. In conclusion, FUS-induced BBB opening and closing was shown to be dependent on the bubble diameter indicating the possibility of specifically designing bubbles to enhance this therapeutic application.

  7. Microbubble-Size Dependence of Focused Ultrasound-Induced Blood–Brain Barrier Opening in Mice In Vivo

    PubMed Central

    Choi, James J.; Feshitan, Jameel A.; Baseri, Babak; Wang, Shougang; Tung, Yao-Sheng; Borden, Mark A.; Konofagou, Elisa E.

    2014-01-01

    The therapeutic efficacy of neurological agents is severely limited, because large compounds do not cross the blood–brain barrier (BBB). Focused ultrasound (FUS) sonication in the presence of microbubbles has been shown to temporarily open the BBB, allowing systemically administered agents into the brain. Until now, polydispersed microbubbles (1–10 μm in diameter) were used, and, therefore, the bubble sizes better suited for inducing the opening remain unknown. Here, the FUS-induced BBB opening dependence on microbubble size is investigated. Bubbles at 1–2 and 4–5 μm in diameter were separately size-isolated using differential centrifugation before being systemically administered in mice (n = 28). The BBB opening pressure threshold was identified by varying the peak-rarefactional pressure amplitude. BBB opening was determined by fluorescence enhancement due to systemically administered, fluorescent-tagged, 3-kDa dextran. The identified threshold fell between 0.30 and 0.46 MPa in the case of 1–2 μm bubbles and between 0.15 and 0.30 MPa in the 4–5 μm case. At every pressure studied, the fluorescence was greater with the 4–5 μm than with the 1–2 μm bubbles. At 0.61 MPa, in the 1–2 μm bubble case, the fluorescence amount and area were greater in the thalamus than in the hippocampus. In conclusion, it was determined that the FUS-induced BBB opening was dependent on both the size distribution in the injected microbubble volume and the brain region targeted. PMID:19846365

  8. Microbubble-size dependence of focused ultrasound-induced blood-brain barrier opening in mice in vivo.

    PubMed

    Choi, James J; Feshitan, Jameel A; Baseri, Babak; Wang, Shougang; Tung, Yao-Sheng; Borden, Mark A; Konofagou, Elisa E

    2010-01-01

    The therapeutic efficacy of neurological agents is severely limited, because large compounds do not cross the blood-brain barrier (BBB). Focused ultrasound (FUS) sonication in the presence of microbubbles has been shown to temporarily open the BBB, allowing systemically administered agents into the brain. Until now, polydispersed microbubbles (1-10 microm in diameter) were used, and, therefore, the bubble sizes better suited for inducing the opening remain unknown. Here, the FUS-induced BBB opening dependence on microbubble size is investigated. Bubbles at 1-2 and 4-5 microm in diameter were separately size-isolated using differential centrifugation before being systemically administered in mice (n = 28). The BBB opening pressure threshold was identified by varying the peak-rarefactional pressure amplitude. BBB opening was determined by fluorescence enhancement due to systemically administered, fluorescent-tagged, 3-kDa dextran. The identified threshold fell between 0.30 and 0.46 MPa in the case of 1-2 microm bubbles and between 0.15 and 0.30 MPa in the 4-5 microm case. At every pressure studied, the fluorescence was greater with the 4-5 mum than with the 1-2 microm bubbles. At 0.61 MPa, in the 1-2 microm bubble case, the fluorescence amount and area were greater in the thalamus than in the hippocampus. In conclusion, it was determined that the FUS-induced BBB opening was dependent on both the size distribution in the injected microbubble volume and the brain region targeted.

  9. Effect of oxygen barrier coatings on oxidation and embrittlement of Ti-6Al-2Sn-4Zr-2Mo foil in heat shield applications

    NASA Technical Reports Server (NTRS)

    Clark, R. K.; Unnam, J.; Wiedemann, K. E.

    1986-01-01

    Because of the loss of ductility with exposure to oxidizing conditions, long time applications of titanium alloys have been limited to temperatures below 700 K and short time applications have been limited to temperatures below 815 K. Oxygen barrier coatings for shielding Ti-6Al-2Sn-4Zr-2Mo alloy from oxidation during exposure to high temperatures were studied using foil gage specimens. The coatings included micrometer-thick sputtered SiO2 and chemical-vapor-deposited silicate layers both with and without an aluminum basecoat. The oxidation rates and resistance to embrittlement of the coated specimens were significantly better than those of the uncoated specimens.

  10. H2O2-dependent substrate oxidation by an engineered diiron site in a bacterial hemerythrin.

    PubMed

    Okamoto, Yasunori; Onoda, Akira; Sugimoto, Hiroshi; Takano, Yu; Hirota, Shun; Kurtz, Donald M; Shiro, Yoshitsugu; Hayashi, Takashi

    2014-04-04

    The O2-binding carboxylate-bridged diiron site in DcrH-Hr was engineered in an effort to perform the H2O2-dependent oxidation of external substrates. A His residue was introduced near the diiron site in place of a conserved residue, Ile119. The I119H variant promotes the oxidation of guaiacol and 1,4-cyclohexadiene upon addition of H2O2.

  11. Temperature Dependent Residual Stress Models for Ultra-High-Temperature Ceramics on High Temperature Oxidation

    NASA Astrophysics Data System (ADS)

    Wang, Ruzhuan; Li, Weiguo

    2016-11-01

    The strength of SiC-depleted layer of ultra-high-temperature ceramics on high temperature oxidation degrades seriously. The research for residual stresses developed within the SiC-depleted layer is important and necessary. In this work, the residual stress evolutions in the SiC-depleted layer and the unoxidized substrate in various stages of oxidation are studied by using the characterization models. The temperature and oxidation time dependent mechanical/thermal properties of each phase in SiC-depleted layer are considered in the models. The study shows that the SiC-depleted layer would suffer from large tensile stresses due to the great temperature changes and the formation of pores on high temperature oxidation. The stresses may lead to the cracking and even the delamination of the oxidation layer.

  12. Oxidative removal of implanted photoresists and barrier metals in semiconductor processing

    NASA Astrophysics Data System (ADS)

    Govindarajan, Rajkumar

    Chemical systems containing oxidants are widely used at various stages in semiconductor processing, particularly for wet cleaning and polishing applications. This dissertation presents a series of studies related to oxidative removal of materials in the Front-End-Of-Line (FEOL) and Chemical Mechanical Planarization (CMP) processes during IC fabrication. In the first part of this study, stripping of photoresists exposed to high dose of ions (1E16 As/cm2) was investigated in activated hydrogen peroxide systems. Stripping of photoresists (PR) exposed to high dose (>1E15/cm2) ion beams is one of the most challenging steps in FEOL processing. This is due to unreactive crust layer that forms on the resist surface during ion implantation. The use of hydrogen peroxide systems activated by metal ion or UV light, for disrupting crust formed on deep UV resist to enable complete removal of crust as well as underlying photoresist was investigated. A systematic evaluation of variables such as hydrogen peroxide and metal ion concentration, UV intensity, temperature and time was conducted and an optimal formulation capable of attacking the crust was developed. A two step process involving pretreatment with activated hydrogen peroxide solution, followed by treatment with sulfuric acid-hydrogen peroxide mixture (SPM) was developed for complete removal of crusted resist films. In the second part of this study, electrochemically enhanced abrasive removal of Ta/TaN films was investigated in solutions containing 2,5 dihydroxy benzene sulfonic acid (DBSA) and potassium iodate (KIO3). This method known as Electrically-assisted Chemical Mechanical Planarization (ECMP) is generating a lot of interest in IC manufacturing. Ta/TaN films were abraded at low pressures (<0.5 psi) on a polyurethane pad under galvanostatic conditions. The effect of variables including pH, KIO3 concentration, and current density has been explored. In the optimized formulation, tantalum and tantalum nitride removal

  13. Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

    SciTech Connect

    Mumm, Daniel

    2013-08-31

    The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leading to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive

  14. Role for Fe(III) minerals in nitrate-dependent microbial U(IV) oxidation

    USGS Publications Warehouse

    Senko, John M.; Mohamed, Yasser; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    Microbiological reduction of soluble U(VI) to insoluble U(IV) is a means of preventing the migration of that element in groundwater, but the presence of nitrate in U(IV)-containing sediments leads to U(IV) oxidation and remobilizaton. Nitrite or iron(III) oxyhydroxides may oxidize U(IV) under nitrate-reducing conditions, and we determined the rate and extent of U(IV) oxidation by these compounds. Fe(III) oxidized U(IV) at a greater rate than nitrite (130 and 10 μM U(IV)/day, respectively). In aquifer sediments, Fe(III) may be produced during microbial nitrate reduction by oxidation of Fe(II) with nitrite, or by enzymatic Fe(II) oxidation coupled to nitrate reduction. To determine which of these mechanisms was dominant, we isolated a nitrate-dependent acetate- and Fe(II)-oxidizing bacterium from a U(VI)- and nitrate-contaminated aquifer. This organism oxidized U(IV) at a greater rate and to a greater extent under acetate-oxidizing (where nitrite accumulated to 50 mM) than under Fe(II)-oxidizing conditions. We show that the observed differences in rate and extent of U(IV) oxidation are due to mineralogical differences between Fe(III) produced by reaction of Fe(II) with nitrite (amorphous) and Fe(III) produced enzymatically (goethite or lepidocrocite). Our results suggest the mineralogy and surface area of Fe(III) minerals produced under nitrate-reducing conditions affect the rate and extent of U(IV) oxidation. These results may be useful for predicting the stability of U(IV) in aquifers.

  15. Size-dependent cytotoxicity of yttrium oxide nanoparticles on primary osteoblasts in vitro

    NASA Astrophysics Data System (ADS)

    Zhou, Guoqiang; Li, Yunfei; Ma, Yanyan; Liu, Zhu; Cao, Lili; Wang, Da; Liu, Sudan; Xu, Wenshi; Wang, Wenying

    2016-05-01

    Yttrium oxide nanoparticles are an excellent host material for the rare earth metals and have high luminescence efficiency providing a potential application in photodynamic therapy and biological imaging. In this study, the effects of yttrium oxide nanoparticles with four different sizes were investigated using primary osteoblasts in vitro. The results demonstrated that the cytotoxicity generated by yttrium oxide nanoparticles depended on the particle size, and smaller particles possessed higher toxicological effects. For the purpose to elucidate the relationship between reactive oxygen species generation and cell damage, cytomembrane integrity, intracellular reactive oxygen species level, mitochondrial membrane potential, cell apoptosis rate, and activity of caspase-3 in cells were then measured. Increased reactive oxygen species level was also observed in a size-dependent way. Thus, our data demonstrated that exposure to yttrium oxide nanoparticles resulted in a size-dependent cytotoxicity in cultured primary osteoblasts, and reactive oxygen species generation should be one possible damage pathway for the toxicological effects produced by yttrium oxide particles. The results may provide useful information for more rational applications of yttrium oxide nanoparticles in the future.

  16. Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

    SciTech Connect

    Laha, Dipranjan; Pramanik, Arindam; Laskar, Aparna; Jana, Madhurya; Pramanik, Panchanan; Karmakar, Parimal

    2014-11-15

    Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Spherical shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain.

  17. Corrosion barriers for silver-based telescope mirrors: comparative study of plasma-enhanced atomic layer deposition and reactive evaporation of aluminum oxide

    NASA Astrophysics Data System (ADS)

    Fryauf, David M.; Phillips, Andrew C.; Kobayashi, Nobuhiko P.

    2015-10-01

    Astronomical telescopes continue to demand high-endurance high-reflectivity silver (Ag) mirrors that can withstand years of exposure in Earth-based observatory environments. We present promising results of improved Ag mirror robustness using plasma-enhanced atomic layer deposition (PEALD) of aluminum oxide (AlOx) as a top barrier layer. Transparent AlOx is suitable for many optical applications; therefore, it has been the initial material of choice for this study. Two coating recipes developed with electron beam ion-assisted deposition (e-beam IAD) of materials including yttrium fluoride, titanium nitride, oxides of yttrium, tantalum, and silicon are used to provide variations in basic Ag mirror structures to compare the endurance of reactive e-beam IAD barriers with PEALD barriers. Samples undergo high temperature/high humidity environmental testing in a controlled environment of 80% humidity at 80°C for 10 days. Environmental testing shows visible results suggesting that the PEALD AlOx barrier offers robust protection against chemical corrosion and moisture permeation. Ag mirror structures were further characterized by reflectivity/absorption before and after deposition of AlOx barriers.

  18. Defect Clustering and Nano-phase Structure Characterization of Multicomponent Rare Earth-Oxide-Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    2004-01-01

    Advanced thermal barrier coatings (TBCs) have been developed by incorporating multicomponent rare earth oxide dopants into zirconia-based thermal barrier coatings to promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nanophases within the coating systems. In this paper, the defect clusters, induced by Nd, Gd, and Yb rare earth dopants in the zirconia-yttria thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The TEM lattice imaging, selected area diffraction (SAD), and electron energy-loss spectroscopy (EELS) analyses demonstrated that the extensive nanoscale rare earth dopant segregation exists in the plasma-sprayed and electron-physical-vapor-deposited (EB PVD) thermal barrier coatings. The nanoscale concentration heterogeneity and the resulting large lattice distortion promoted the formation of parallel and rotational defective lattice clusters in the coating systems. The presence of the 5-to 100-nm-sized defect clusters and nanophases is believed to be responsible for the significant reduction of thermal conductivity, improved sintering resistance, and long-term high temperature stability of the advanced thermal barrier coating systems.

  19. Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

    PubMed Central

    Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

    2015-01-01

    Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

  20. Transparent bionanocomposite films based on chitosan and TEMPO-oxidized cellulose nanofibers with enhanced mechanical and barrier properties.

    PubMed

    Soni, Bhawna; Hassan, El Barbary; Schilling, M Wes; Mahmoud, Barakat

    2016-10-20

    The development of biobased active films for use in food packaging is increasing due to low cost, environmental appeal, renewability and availability. The objective of this research was to develop an effective and complete green approach for the production of bionanocomposite films with enhanced mechanical and barrier properties. This was accomplished by incorporating TEMPO-oxidized cellulose nanofibers (2,2,6,6-tetramethylpiperidine-1-oxyl radical) into a chitosan matrix. An aqueous suspension of chitosan (100-75wt%), sorbitol (25wt%) and TEMPO-oxidized cellulose nanofibers (TEMPO-CNFs, 0-25wt%) were cast in an oven at 40°C for 2-4days. Films were preconditioned at 25°C and 50% RH for characterization. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermogravimetric analysis (TGA-DTG) and X-ray diffraction (XRD). Incorporation of TEMPO-CNFs enhanced the mechanical strength of the films due to the high aspect ratio (3-20nm width, and 10-100nm length) of TEMPO-CNFs and strong interactions with the chitosan matrix. Oxygen and water vapor transmission rates for films that are prepared with chitosan and TEMPO-CNFs (15-25wt%) were significantly reduced. Furthermore, these bionanocomposite films had good thermal stability. Use of TEMPO-CNFs in this method makes it possible to produce bionanocomposite films that are flexible, transparent, and thus have potential in food packaging applications.

  1. Optimizing superparamagnetic iron oxide nanoparticles as drug carriers using an in vitro blood–brain barrier model

    PubMed Central

    Shi, Di; Mi, Gujie; Bhattacharya, Soumya; Nayar, Suprabha; Webster, Thomas J

    2016-01-01

    In the current study, an optimized in vitro blood–brain barrier (BBB) model was established using mouse brain endothelial cells (b.End3) and astrocytes (C8-D1A). Before measuring the permeability of superparamagnetic iron oxide nanoparticle (SPION) samples, the BBB was first examined and confirmed by an immunofluorescent stain and evaluating the transendothelial electrical resistance. After such confirmation, the permeability of the following five previously synthesized SPIONs was determined using this optimized BBB model: 1) GGB (synthesized using glycine, glutamic acid, and bovine serum albumin [BSA]), 2) GGC (glycine, glutamic acid, and collagen), 3) GGP (glycine, glutamic acid, and polyvinyl alcohol), 4) BPC (BSA, polyethylene glycol, and collagen), and 5) CPB (collagen, polyvinyl alcohol, and BSA). More importantly, after the permeability test, transmission electron microscopy thin section technology was used to investigate the mechanism behind this process. Transmission electron microscopy thin section images supported the hypothesis that collagen-coated CPB SPIONs displayed better cellular uptake than glycine and glutamine acid-coated GGB SPIONs. Such experimental data demonstrated how one can modify SPIONs to better deliver drugs to the brain to treat a wide range of neurological disorders. PMID:27799764

  2. The effect of oxygen and water vapor on nitric oxide conversion with a dielectric barrier discharge reactor

    SciTech Connect

    Yin, S.E.; Sun, B.M.; Gao, X.D.; Xiao, H.P.

    2009-12-15

    The effect of O{sub 2} and H{sub 2}O vapor on the Nitric oxide (NO) removal rate, the NO{sub 2} generation rate and the discharge characteristics were investigated using the dielectric barrier discharge (DBD) reactor at 1 atm pressure and at room temperature (20{sup o}). The results showed that the O{sub 2} present in the flue gas always hampered the removal of NO and the generation of N{sub 2}O, but that the O{sub 2} could enhance the generation of NO{sub 2} in the NO/N{sub 2}/O{sub 2} mixtures. Furthermore, with the increase of oxygen, the average discharge current gradually decreases in the reactor. The H{sub 2}O present in N-2/NO hindered the removal of NO and the generation of NO{sub 2} but had no impact on the average discharge current in the reactor in the NO/N{sub 2}/H{sub 2}O mixtures in which the HNO{sub 2} and HNO{sub 3} was detected. The energy efficiency of the DBD used to remove the NO from the flue gas was also estimated.

  3. Optimizing superparamagnetic iron oxide nanoparticles as drug carriers using an in vitro blood-brain barrier model.

    PubMed

    Shi, Di; Mi, Gujie; Bhattacharya, Soumya; Nayar, Suprabha; Webster, Thomas J

    In the current study, an optimized in vitro blood-brain barrier (BBB) model was established using mouse brain endothelial cells (b.End3) and astrocytes (C8-D1A). Before measuring the permeability of superparamagnetic iron oxide nanoparticle (SPION) samples, the BBB was first examined and confirmed by an immunofluorescent stain and evaluating the transendothelial electrical resistance. After such confirmation, the permeability of the following five previously synthesized SPIONs was determined using this optimized BBB model: 1) GGB (synthesized using glycine, glutamic acid, and bovine serum albumin [BSA]), 2) GGC (glycine, glutamic acid, and collagen), 3) GGP (glycine, glutamic acid, and polyvinyl alcohol), 4) BPC (BSA, polyethylene glycol, and collagen), and 5) CPB (collagen, polyvinyl alcohol, and BSA). More importantly, after the permeability test, transmission electron microscopy thin section technology was used to investigate the mechanism behind this process. Transmission electron microscopy thin section images supported the hypothesis that collagen-coated CPB SPIONs displayed better cellular uptake than glycine and glutamine acid-coated GGB SPIONs. Such experimental data demonstrated how one can modify SPIONs to better deliver drugs to the brain to treat a wide range of neurological disorders.

  4. Graphite oxide incorporated crosslinked polyvinyl alcohol and sulfonated styrene nanocomposite membrane as separating barrier in single chambered microbial fuel cell

    NASA Astrophysics Data System (ADS)

    Rudra, Ruchira; Kumar, Vikash; Pramanik, Nilkamal; Kundu, Patit Paban

    2017-02-01

    Different membranes with varied molar concentrations of graphite oxide (GO), 'in situ' polymerized sulfonated polystyrene (SS) and glutaraldehyde (GA) cross linked polyvinyl alcohol (PVA), have been analyzed as an effective and low cost nanocomposite barrier in single chambered microbial fuel cells (MFCs). The synthesized composite membranes, namely GO0.2, GO0.4 and GO0.6 exhibited comparatively better results with reduced water uptake (WU) and swelling ratios (SR) over the native PVA. The variation in properties is illustrated with membrane analyses, where GO0.4 showed an increased proton conductivity (PC) and ion exchange capacity (IEC) of 0.128 S cm-1 and 0.33 meq g-1 amongst all of the used membranes. In comparison, reduced oxygen diffusivity with lower water uptake showed a two-fold decrease in GO0.4 over pure PVA membrane (∼2.09 × 10-4 cm s-1). A maximum power density of 193.6 mW m-2 (773.33 mW m-3) with a current density of 803.33 mA m-2 were observed with GO0.4 fitted MFC, where ∼81.89% of chemical oxygen demand (COD) was removed using mixed firmicutes, as biocatalyst, in 25 days operation. In effect, the efficacy of GO incorporated crosslinked PVA and SS nanocomposite membrane has been evaluated as a polymer electrolyte membrane for harnessing bio-energy from single chambered MFCs.

  5. The topical use of non-thermal dielectric barrier discharge (DBD): nitric oxide related effects on human skin.

    PubMed

    Heuer, Kiara; Hoffmanns, Martin A; Demir, Erhan; Baldus, Sabrina; Volkmar, Christine M; Röhle, Mirco; Fuchs, Paul C; Awakowicz, Peter; Suschek, Christoph V; Opländer, Christian

    2015-01-30

    Dielectric barrier discharge (DBD) devices generate air plasma above the skin containing active and reactive species including nitric oxide (NO). Since NO plays an essential role in skin physiology, a topical application of NO by plasma may be useful in the treatment of skin infections, impaired microcirculation and wound healing. Thus, after safety assessments of plasma treatment using human skin specimen and substitutes, NO-penetration through the epidermis, the loading of skin tissue with NO-derivates in vitro and the effects on human skin in vivo were determined. After the plasma treatment (0-60 min) of skin specimen or reconstructed epidermis no damaging effects were found (TUNEL/MTT). By Franz diffusion cell experiments plasma-induced NO penetration through epidermis and dermal enrichment with NO related species (nitrite 6-fold, nitrate 7-fold, nitrosothiols 30-fold) were observed. Furthermore, skin surface was acidified (~pH 2.7) by plasma treatment (90 s). Plasma application on the forearms of volunteers increased microcirculation fourfold in 1-2 mm and twofold in 6-8 mm depth in the treated skin areas. Regarding the NO-loading effects, skin acidification and increase in dermal microcirculation, plasma devices represent promising tools against chronic/infected wounds. However, efficacy of plasma treatment needs to be quantified in further studies and clinical trials.

  6. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    PubMed Central

    Fenske, Daniela; Bardenhagen, Ingo; Westphal, Anne; Knipper, Martin; Plaggenborg, Thorsten; Kolny-Olesiak, Joanna; Parisi, Jürgen

    2015-01-01

    Summary Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx + oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II) glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD) measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II) glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM) and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species. PMID:25671151

  7. Applied voltage dependence of nano-oxidation of ferromagnetic thin films using atomic force microscope

    NASA Astrophysics Data System (ADS)

    Takemura, Yasushi; Kidaka, Seiichi; Watanabe, Keizo; Nasu, Yasuaki; Yamada, Tsutomu; Shirakashi, Jun-ichi

    2003-05-01

    Nanodots of Ni, CoFe, and Cr oxide were fabricated by the nano-oxidation technique using atomic force microscope. The dot size was controlled from 40 to 200 nm by changing the pulse voltage applied to the cantilever from 2 to 10 V. In order to evaluate the size of the nanostructures quantitatively, the electric field emitted from the cantilever was calculated. The threshold electric field strength was defined as the minimum strength to promote the oxidation. The threshold field strength of the order of 107 V/m was derived by fitting the experimental results. The voltage dependence of the size of fabricated Cr-oxide dots was fitted well by the calculation. The dot size of the ferromagnet-based oxide was fluctuating and did not agree with the calculation. From the theoretical analysis, it was suggested that the size of the nanostructures did not depend on the distance between the cantilever and film surface, but significantly depended on the curvature radius of the cantilever.

  8. A photoemission study of the effectiveness of nickel, manganese, and cobalt based corrosion barriers for silicon photo-anodes during water oxidation

    NASA Astrophysics Data System (ADS)

    O'Connor, Robert; Bogan, Justin; McCoy, Anthony; Byrne, Conor; Hughes, Greg

    2016-05-01

    Silicon is an attractive material for solar water splitting applications due to its abundance and its capacity to absorb a large fraction of incident solar radiation. However, it has not received as much attention as other materials due to its tendency to oxidize very quickly in aqueous environments, particularly when it is employed as the anode where it drives the oxygen evolution reaction. In recent years, several works have appeared in the literature examining the suitability of thin transition metal oxide films grown on top of the silicon to act as a corrosion barrier. The film should be transparent to solar radiation, allow hole transport from the silicon surface to the electrolyte, and stop the diffusion of oxygen from the electrolyte back to the silicon. In this work, we compare Mn-oxide, Co-oxide, and Ni-oxide thin films grown using physical vapor deposition in order to evaluate which material offers the best combination of photocurrent and corrosion protection. In addition to the electrochemical data, we also present a detailed before-and-after study of the surface chemistry of the films using x-ray photoelectron spectroscopy. This approach allows for a comprehensive analysis of the mechanisms by which the corrosion barriers protect the underlying silicon, and how they degrade during the water oxidation reaction.

  9. Permeability dependence study of the focused ultrasound-induced blood-brain barrier opening at distinct pressures and microbubble diameters using DCE-MRI.

    PubMed

    Vlachos, Fotios; Tung, Yao-Sheng; Konofagou, Elisa

    2011-09-01

    Blood-brain barrier opening using focused ultrasound and microbubbles has been experimentally established as a noninvasive and localized brain drug delivery technique. In this study, the permeability of the opening is assessed in the murine hippocampus after the application of focused ultrasound at three different acoustic pressures and microbubble sizes. Using dynamic contrast-enhanced MRI, the transfer rates were estimated, yielding permeability maps and quantitative K(trans) values for a predefined region of interest. The volume of blood-brain barrier opening according to the K(trans) maps was proportional to both the pressure and the microbubble diameter. A K(trans) plateau of ∼0.05 min(-1) was reached at higher pressures (0.45 and 0.60 MPa) for the larger sized bubbles (4-5 and 6-8 μm), which was on the same order as the K(trans) of the epicranial muscle (no barrier). Smaller bubbles (1-2 μm) yielded significantly lower permeability values. A small percentage (7.5%) of mice showed signs of damage under histological examination, but no correlation with permeability was established. The assessment of the blood-brain barrier permeability properties and their dependence on both the pressure and the microbubble diameter suggests that K(trans) maps may constitute an in vivo tool for the quantification of the efficacy of the focused ultrasound-induced blood-brain barrier opening.

  10. Thermal barrier coating life prediction model development

    NASA Technical Reports Server (NTRS)

    Cruse, T. A.; Stewart, S. E.; Ortiz, M.

    1988-01-01

    A life prediction model for correlating the spallation life of ceramic thermal barrier coatings is developed which includes both cyclic and time-dependent damage. The cyclic damage is related to the calculated cyclic inelastic strain range, while the time-dependent damage is related to the oxidation kinetics at the bond-ceramic interface. The cyclic inelastic strain range is calculated using a modified form of the Walker viscoplastic material model; calculation of the oxidation kinetics is based on traditional oxidation algorithms using experimentally determined parameters. The correlation between the actual and predicted spallation lives is within a factor of 3.

  11. Neutron transfer versus inelastic surface vibrations in the enhancement of sub-barrier fusion excitation function data and the energy dependent Woods-Saxon potential

    NASA Astrophysics Data System (ADS)

    Singh Gautam, Manjeet

    2015-02-01

    This work deeply analyzed the relative importance of the neutron transfer channels and inelastic surface vibrations of colliding nuclei in the sub-barrier fusion enhancement of various heavy ion systems using an energy dependent Woods-Saxon potential (EDWSP) model in conjunction with a one-dimensional Wong formula and the coupled channel formulation using the code CCFULL. The multi-phonon vibrational states of colliding nuclei and the nucleon transfer channels are found to be dominant internal degrees of freedom. The coupling between the relative motion of reactants and these relevant channels produces anomalously large sub-barrier fusion enhancement over the expectations of the one-dimensional barrier penetration model. In some cases, the influence of neutron transfer dominates over the couplings to low lying surface vibrational states of collision partners. Furthermore, the effects of coupling to inelastic surface excitations and the impact of neutron transfer channels with positive ground state Q-values are imitated due to energy dependence in the Woods-Saxon potential. In the EDWSP model calculations, a wide range for the diffuseness parameter, which is much larger than the value extracted from the elastic scattering data, is needed to account for the observed fusion enhancement in the close vicinity of the Coulomb barrier.

  12. Visualization of Oxidative Stress Induced by Experimental Periodontitis in Keap1-Dependent Oxidative Stress Detector-Luciferase Mice

    PubMed Central

    Kataoka, Kota; Ekuni, Daisuke; Tomofuji, Takaaki; Irie, Koichiro; Kunitomo, Muneyoshi; Uchida, Yoko; Fukuhara, Daiki; Morita, Manabu

    2016-01-01

    The aim of this study was to investigate whether a Keap1-dependent oxidative stress detector-luciferase (OKD-LUC) mouse model would be useful for the visualization of oxidative stress induced by experimental periodontitis. A ligature was placed around the mandibular first molars for seven days to induce periodontitis. Luciferase activity was measured with an intraperitoneal injection of d-luciferin on days 0, 1, and 7. The luciferase activity in the periodontitis group was significantly greater than that in the control group at seven days. The expressions of heme oxygenase-1 (HO-1) and malondialdehyde in periodontal tissue were significantly higher in the periodontitis group than in the control group. Immunofluorescent analysis confirmed that the nuclear translocation of nuclear factor erythroid 2-related factor 2 (Nrf2) occurred more frequently in the periodontitis group than in the control group. This study found that under oxidative stress induced by experimental periodontitis, the Nrf2/antioxidant defense pathway was activated and could be visualized from the luciferase activity in the OKD-LUC model. Thus, the OKD-LUC mouse model may be useful for exploring the mechanism underlying the relationship between the Nrf2/antioxidant defense pathway and periodontitis by enabling the visualization of oxidative stress over time. PMID:27854327

  13. Oxidative stress activates FUS1 and RLM1 transcription in the yeast Saccharomyces cerevisiae in an oxidant-dependent Manner.

    PubMed

    Staleva, Liliana; Hall, Andrea; Orlow, Seth J

    2004-12-01

    Mating in haploid Saccharomyces cerevisiae occurs after activation of the pheromone response pathway. Biochemical components of this pathway are involved in other yeast signal transduction networks. To understand more about the coordination between signaling pathways, we used a "chemical genetic" approach, searching for compounds that would activate the pheromone-responsive gene FUS1 and RLM1, a reporter for the cell integrity pathway. We found that catecholamines (l-3,4-hydroxyphenylalanine [l-dopa], dopamine, adrenaline, and noradrenaline) elevate FUS1 and RLM1 transcription. N-Acetyl-cysteine, a powerful antioxidant in yeast, completely reversed this effect, suggesting that FUS1 and RLM1 activation in response to catecholamines is a result of oxidative stress. The oxidant hydrogen peroxide also was found to activate transcription of an RLM1 reporter. Further genetic analysis combined with immunoblotting revealed that Kss1, one of the mating mitogen-activated protein kinases (MAPKs), and Mpk1, an MAPK of the cell integrity pathway, participated in l-dopa-induced stimulation of FUS1 and RLM1 transcription. We also report that Mpk1 and Hog1, the high osmolarity MAPK, were phosphorylated upon induction by hydrogen peroxide. Together, our results demonstrate that cells respond to oxidative stress via different signal transduction machinery dependent upon the nature of the oxidant.

  14. Na(+)-dependent glutamate transporters (EAAT1, EAAT2, and EAAT3) of the blood-brain barrier. A mechanism for glutamate removal.

    PubMed

    O'Kane, R L; Martínez-López, I; DeJoseph, M R; Viña, J R; Hawkins, R A

    1999-11-05

    Na(+)-dependent transporters for glutamate exist on astrocytes (EAAT1 and EAAT2) and neurons (EAAT3). These transporters presumably assist in keeping the glutamate concentration low in the extracellular fluid of brain. Recently, Na(+)-dependent glutamate transport was described on the abluminal membrane of the blood-brain barrier. To determine whether the above-mentioned transporters participate in glutamate transport of the blood-brain barrier, total RNA was extracted from bovine cerebral capillaries. cDNA for EAAT1, EAAT2, and EAAT3 was observed, indicating that mRNA was present. Western blot analysis demonstrated all three transporters were expressed on abluminal membranes, but none was detectable on luminal membranes of the blood-brain barrier. Measurement of transport kinetics demonstrated voltage dependence, K(+)-dependence, and an apparent K(m) of 14 microM (aggregate of the three transporters) at a transmembrane potential of -61 mV. Inhibition of glutamate transport was observed using inhibitors specific for EAAT2 (kainic acid and dihydrokainic acid) and EAAT3 (cysteine). The relative activity of the three transporters was found to be approximately 1:3:6 for EAAT1, EAAT2, and EAAT3, respectively. These transporters may assist in maintaining low glutamate concentrations in the extracellular fluid.

  15. CYP2E1-dependent hepatotoxicity and oxidative damage after ethanol administration in human primary hepatocytes

    PubMed Central

    Liu, Lie-Gang; Yan, Hong; Yao, Ping; Zhang, Wen; Zou, Li-Jun; Song, Fang-Fang; Li, Ke; Sun, Xiu-Fa

    2005-01-01

    AIM: To observe the relationship between ethanol-induced oxidative damage in human primary cultured hepatocytes and cytochrome P450 2E1 (CYP2E1) activity, in order to address if inhibition of CYP2E1 could attenuate ethanol-induced cellular damage. METHODS: The dose-dependent (25-100 mmol/L) and time-dependent (0-24 h) exposures of primary human cultured hepatocytes to ethanol were carried out. CYP2E1 activity and protein expression were detected by spectrophotometer and Western blot analysis respectively. Hepatotoxicity was investigated by determination of lactate dehydrogenase (LDH) and aspartate transaminase (AST) level in hepatocyte culture supernatants, as well as the intracellular formation of malondialdehyde (MDA). RESULTS: A dose-and time-dependent response between ethanol exposure and CYP2E1 activity in human hepatocytes was demonstrated. Moreover, there was a time-dependent increase of CYP2E1 protein after 100 mmol/L ethanol exposure. Meanwhile, ethanol exposure of hepatocytes caused a time-dependent increase of cellular MDA level, LDH, and AST activities in supernatants. Furthermore, the inhibitor of CYP2E1, diallyl sulfide (DAS) could partly attenuate the increases of MDA, LDH, and AST in human hepatocytes. CONCLUSION: A positive relationship between ethanol-induced oxidative damage in human primary cultured hepatocytes and CYP2E1 activity was exhibited, and the inhibition of CYP2E1 could partly attenuate ethanol-induced oxidative damage. PMID:16052683

  16. Sulfur globule oxidation in green sulfur bacteria is dependent on the dissimilatory sulfite reductase system.

    PubMed

    Holkenbrink, Carina; Barbas, Santiago Ocón; Mellerup, Anders; Otaki, Hiroyo; Frigaard, Niels-Ulrik

    2011-04-01

    Green sulfur bacteria (GSB) oxidize sulfide and thiosulfate to sulfate, with extracellular globules of elemental sulfur as an intermediate. Here we investigated which genes are involved in the formation and consumption of these sulfur globules in the green sulfur bacterium Chlorobaculum tepidum. We show that sulfur globule oxidation is strictly dependent on the dissimilatory sulfite reductase (DSR) system. Deletion of dsrM/CT2244 or dsrT/CT2245, or the two dsrCABL clusters (CT0851-CT0854, CT2247-2250), abolished sulfur globule oxidation and prevented formation of sulfate from sulfide, whereas deletion of dsrU/CT2246 had no effect. The DSR system also seems to be involved in the formation of thiosulfate, because thiosulfate was released from wild-type cells during sulfide oxidation, but not from the dsr mutants. The dsr mutants incapable of complete substrate oxidation oxidized sulfide and thiosulfate about twice as fast as the wild-type, while having only slightly lower growth rates (70-80 % of wild-type). The increased oxidation rates seem to compensate for the incomplete substrate oxidation to satisfy the requirement for reducing equivalents during growth. A mutant in which two sulfide : quinone oxidoreductases (sqrD/CT0117 and sqrF/CT1087) were deleted exhibited a decreased sulfide oxidation rate (~50 % of wild-type), yet formation and consumption of sulfur globules were not affected. The observation that mutants lacking the DSR system maintain efficient growth suggests that the DSR system is dispensable in environments with sufficiently high sulfide concentrations. Thus, the DSR system in GSB may have been acquired by horizontal gene transfer as a response to a need for enhanced substrate utilization in sulfide-limiting habitats.

  17. DEGRADATION OF SM2ZR2O7 THERMAL BARRIER COATING CAUSED BY CALCIUM-MAGNESIUM-ALUMINUM-SILICON OXIDE (CMAS) DEPOSITION

    SciTech Connect

    Wang, Honglong; Sheng, Zhizhi; Tarwater, Emily; Zhang, Xingxing; Dasgupta, Sudip; Fergus, Jeffrey

    2015-03-16

    Rare earth zirconates are promising materials for use as thermal barrier coatings in gas turbine engines. Among the lanthanide zirconate materials, Sm2Zr2O7 with the pyrochlore structure has lower thermal conductivity and better corrosion resistance against calcium-magnesium-aluminum-silicon oxide (CMAS). In this work, after reaction with CMAS, the pyrochlore structure transforms to the cubic fluorite structure and Ca2Sm8(SiO4)6O2 forms in elongated grain.

  18. Selenate-dependent anaerobic arsenite oxidation by a bacterium from Mono Lake, California.

    PubMed

    Fisher, Jenny C; Hollibaugh, James T

    2008-05-01

    Arsenate was produced when anoxic Mono Lake water samples were amended with arsenite and either selenate or nitrate. Arsenite oxidation did not occur in killed control samples or live samples with no added terminal electron acceptor. Potential rates of anaerobic arsenite oxidation with selenate were comparable to those with nitrate ( approximately 12 to 15 mumol.liter(-1) h(-1)). A pure culture capable of selenate-dependent anaerobic arsenite oxidation (strain ML-SRAO) was isolated from Mono Lake water into a defined salts medium with selenate, arsenite, and yeast extract. This strain does not grow chemoautotrophically, but it catalyzes the oxidation of arsenite during growth on an organic carbon source with selenate. No arsenate was produced in pure cultures amended with arsenite and nitrate or oxygen, indicating that the process is selenate dependent. Experiments with washed cells in mineral medium demonstrated that the oxidation of arsenite is tightly coupled to the reduction of selenate. Strain ML-SRAO grows optimally on lactate with selenate or arsenate as the electron acceptor. The amino acid sequences deduced from the respiratory arsenate reductase gene (arrA) from strain ML-SRAO are highly similar (89 to 94%) to those from two previously isolated Mono Lake arsenate reducers. The 16S rRNA gene sequence of strain ML-SRAO places it within the Bacillus RNA group 6 of gram-positive bacteria having low G+C content.

  19. Nano rare-earth oxides induced size-dependent vacuolization: an independent pathway from autophagy

    PubMed Central

    Zhang, Ying; Yu, Chenguang; Huang, Guanyi; Wang, Changli; Wen, Longping

    2010-01-01

    Four rare earth oxides have been shown to induce autophagy. Interestingly, we often noticed plentiful vacuolization, which was not always involved in this autophagic process. In this study, we investigated three other rare-earth elements, including Yttrium (Y), Ytterbium (Yb), and Lanthanum (La). Autophagic effect could be induced by all of them but only Y2O3 and Yb2O3 could cause massive vacuolization. Y2O3 and Yb2O3 treated by sonication or centrifugation to reduce particle size were used to test vacuolization level in HeLa cell lines. The results showed that rare earth oxides-induced vacuolization is size-dependent and differs from autophagic pathway. To further clarify the characteristics of this autophagic process, we used MEF Atg-5 (autophagy associated gene 5) knockout cell line, and the result showed that the autophagic process induced by rare earth oxides is Atg-5-dependent and the observed vacuolization was independent from autophagy. Similar results could also be observed in our tests on 3-methyladenine(3-MA), a well-known autophagy inhibitor. In conclusion, for the first time, we clarified the relationship between massive vacuolization and autophagic process induced by rare earth oxides and pointed out the size effect of rare earth oxides on the formation of vacuoles, which give clues to further investigation on the mechanisms underlying their biological effects. PMID:20856835

  20. Grain and burnup dependence of spent fuel oxidation: geological repository impact

    SciTech Connect

    Hanson, B. D.; Kansa, E. J.; Stoot, R.B.

    1998-10-15

    Further refinements to the oxidation model of Stout et al. have been made. The present model incorporates the burnup dependence of the oxidation rate in addition to an allowance for a distribution of grain sizes. The model was tested by comparing the model results with the oxidation histories of spent fuel samples oxidized in Thermogravimetric Analysis (TGA) or Oven Dry-Bath (ODB) experiments. The comparison between the experimental and model results are remarkably close and confirm the assumption that grain-size distributions and activation energies are the important parameters to predicting oxidation behavior. The burnup dependence of the activation energy was shown to have a greater effect than decreasing the effective grain size in suppressing the rate of the reaction U{sub 4}O{sub 9}(rightwards arrow)U{sub 3} O{sub 4}. Model results predict that U{sub 3}O{sub 8} formation of spent fuels exposed to oxygen will be suppressed even for high burnup fuels that have undergone restructuring in the rim region, provided the repository temperature is kept sufficient.

  1. Nano rare-earth oxides induced size-dependent vacuolization: an independent pathway from autophagy.

    PubMed

    Zhang, Ying; Yu, Chenguang; Huang, Guanyi; Wang, Changli; Wen, Longping

    2010-09-07

    Four rare earth oxides have been shown to induce autophagy. Interestingly, we often noticed plentiful vacuolization, which was not always involved in this autophagic process. In this study, we investigated three other rare-earth elements, including Yttrium (Y), Ytterbium (Yb), and Lanthanum (La). Autophagic effect could be induced by all of them but only Y(2)O(3) and Yb(2)O(3) could cause massive vacuolization. Y(2)O(3) and Yb(2)O(3) treated by sonication or centrifugation to reduce particle size were used to test vacuolization level in HeLa cell lines. The results showed that rare earth oxides-induced vacuolization is size-dependent and differs from autophagic pathway. To further clarify the characteristics of this autophagic process, we used MEF Atg-5 (autophagy associated gene 5) knockout cell line, and the result showed that the autophagic process induced by rare earth oxides is Atg-5-dependent and the observed vacuolization was independent from autophagy. Similar results could also be observed in our tests on 3-methyladenine(3-MA), a well-known autophagy inhibitor. In conclusion, for the first time, we clarified the relationship between massive vacuolization and autophagic process induced by rare earth oxides and pointed out the size effect of rare earth oxides on the formation of vacuoles, which give clues to further investigation on the mechanisms underlying their biological effects.

  2. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    2003-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  3. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    1990-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi- component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma- sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia-yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging fiom 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  4. Microbially catalyzed nitrate-dependent metal/radionuclide oxidation in shallow subsurface sediments

    NASA Astrophysics Data System (ADS)

    Weber, K.; Healy, O.; Spanbauer, T. L.; Snow, D. D.

    2011-12-01

    Anaerobic, microbially catalyzed nitrate-dependent metal/radionuclide oxidation has been demonstrated in a variety of sediments, soils, and groundwater. To date, studies evaluating U bio-oxidation and mobilization have primarily focused on anthropogenically U contaminated sites. In the Platte River Basin U originating from weathering of uranium-rich igneous rocks in the Rocky Mountains was deposited in shallow alluvial sediments as insoluble reduced uranium minerals. These reduced U minerals are subject to reoxidation by available oxidants, such nitrate, in situ. Soluble uranium (U) from natural sources is a recognized contaminant in public water supplies throughout the state of Nebraska and Colorado. Here we evaluate the potential of anaerobic, nitrate-dependent microbially catalyzed metal/radionuclide oxidation in subsurface sediments near Alda, NE. Subsurface sediments and groundwater (20-64ft.) were collected from a shallow aquifer containing nitrate (from fertilizer) and natural iron and uranium. The reduction potential revealed a reduced environment and was confirmed by the presence of Fe(II) and U(IV) in sediments. Although sediments were reduced, nitrate persisted in the groundwater. Nitrate concentrations decreased, 38 mg/L to 30 mg/L, with increasing concentrations of Fe(II) and U(IV). Dissolved U, primarily as U(VI), increased with depth, 30.3 μg/L to 302 μg/L. Analysis of sequentially extracted U(VI) and U(IV) revealed that virtually all U in sediments existed as U(IV). The presence of U(IV) is consistent with reduced Fe (Fe(II)) and low reduction potential. The increase in aqueous U concentrations with depth suggests active U cycling may occur at this site. Tetravalent U (U(IV)) phases are stable in reduced environments, however the input of an oxidant such as oxygen or nitrate into these systems would result in oxidation. Thus co-occurrence of nitrate suggests that nitrate could be used by bacteria as a U(IV) oxidant. Most probable number

  5. Gap Junction Proteins in the Blood-Brain Barrier Control Nutrient-Dependent Reactivation of Drosophila Neural Stem Cells

    PubMed Central

    Spéder, Pauline; Brand, Andrea H.

    2014-01-01

    Summary Neural stem cells in the adult brain exist primarily in a quiescent state but are reactivated in response to changing physiological conditions. How do stem cells sense and respond to metabolic changes? In the Drosophila CNS, quiescent neural stem cells are reactivated synchronously in response to a nutritional stimulus. Feeding triggers insulin production by blood-brain barrier glial cells, activating the insulin/insulin-like growth factor pathway in underlying neural stem cells and stimulating their growth and proliferation. Here we show that gap junctions in the blood-brain barrier glia mediate the influence of metabolic changes on stem cell behavior, enabling glia to respond to nutritional signals and reactivate quiescent stem cells. We propose that gap junctions in the blood-brain barrier are required to translate metabolic signals into synchronized calcium pulses and insulin secretion. PMID:25065772

  6. Wet oxidation of Al{sub x}GA{sub 1-x}As: arsenic barriers on the road to mis

    SciTech Connect

    Ashby, C.I.H.; Sullivan, J.P.; Newcomer, P.P.; Missert, N.A.; Hou, H.Q.; Hammons, B.E.; Baca, A.G.

    1997-02-01

    Three characteristic regimes were identified during wet thermal oxidation of AlxGa(1-x)As (x=1 to 0.90) on GaAs: oxidation of Al and Ga in the alloy to form to an amorphous oxide layer, formation and elimination of elemental As and of amorphous As2O3, and crystallization of the oxide film. Residual As can produce up to a 100fold increase in leakage current and a 30% increase in bulk dielectric constant. Very low As levels produce partial Fermi-level pinning at the oxidized AlxGa(1-x)As/GaAs interface. Local Schottky- barrier pinning of the Fermi level at As precipitates at the oxide/GaAs interface may be the source of the apparent high interface state density. The presence of thermodynamically favored interfacial As may impose a fundamental limit on the application of AlGaAs wet oxidation for achieving MIS devices without post-oxidation processing to remove the residual As from the interface.

  7. Anomalous quantum efficiency for photoconduction and its power dependence in metal oxide semiconductor nanowires.

    PubMed

    Chen, R S; Wang, W C; Lu, M L; Chen, Y F; Lin, H C; Chen, K H; Chen, L C

    2013-08-07

    The quantum efficiency and carrier lifetime that decide the photoconduction (PC) efficiencies in the metal oxide semiconductor nanowires (NWs) have been investigated. The experimental result surprisingly shows that the SnO2, TiO2, WO3, and ZnO NWs reveal extraordinary quantum efficiencies in common, which are over one to three orders of magnitude lower than the theoretical expectation. The surface depletion region (SDR)-controlled photoconductivity is proposed to explain the anomalous quantum efficiency and its power dependence. The inherent difference between the metal oxide nanostructures such as carrier lifetime, carrier concentration, and dielectric constant leading to the distinct PC performance and behavior are also discussed.

  8. The oxidative costs of reproduction are group-size dependent in a wild cooperative breeder

    PubMed Central

    Cram, Dominic L.; Blount, Jonathan D.; Young, Andrew J.

    2015-01-01

    Life-history theory assumes that reproduction entails a cost, and research on cooperatively breeding societies suggests that the cooperative sharing of workloads can reduce this cost. However, the physiological mechanisms that underpin both the costs of reproduction and the benefits of cooperation remain poorly understood. It has been hypothesized that reproductive costs may arise in part from oxidative stress, as reproductive investment may elevate exposure to reactive oxygen species, compromising survival and future reproduction and accelerating senescence. However, experimental evidence of oxidative costs of reproduction in the wild remains scarce. Here, we use a clutch-removal experiment to investigate the oxidative costs of reproduction in a wild cooperatively breeding bird, the white-browed sparrow weaver, Plocepasser mahali. Our results reveal costs of reproduction that are dependent on group size: relative to individuals in groups whose eggs were experimentally removed, individuals in groups that raised offspring experienced an associated cost (elevated oxidative damage and reduced body mass), but only if they were in small groups containing fewer or no helpers. Furthermore, during nestling provisioning, individuals that provisioned at higher rates showed greater within-individual declines in body mass and antioxidant protection. Our results provide rare experimental evidence that reproduction can negatively impact both oxidative status and body mass in the wild, and suggest that these costs can be mitigated in cooperative societies by the presence of additional helpers. These findings have implications for our understanding of the energetic and oxidative costs of reproduction, and the benefits of cooperation in animal societies. PMID:26582023

  9. Opposing effects of oxidative challenge and carotenoids on antioxidant status and condition-dependent sexual signalling.

    PubMed

    Tomášek, Oldřich; Gabrielová, Barbora; Kačer, Petr; Maršík, Petr; Svobodová, Jana; Syslová, Kamila; Vinkler, Michal; Albrecht, Tomáš

    2016-03-22

    Several recent hypotheses consider oxidative stress to be a primary constraint ensuring honesty of condition-dependent carotenoid-based signalling. The key testable difference between these hypotheses is the assumed importance of carotenoids for redox homeostasis, with carotenoids being either antioxidant, pro-oxidant or unimportant. We tested the role of carotenoids in redox balance and sexual signalling by exposing adult male zebra finches (Taeniopygia guttata) to oxidative challenge (diquat dibromide) and manipulating carotenoid intake. As the current controversy over the importance of carotenoids as antioxidants could stem from the hydrophilic basis of commonly-used antioxidant assays, we used the novel measure of in vivo lipophilic antioxidant capacity. Oxidative challenge reduced beak pigmentation but elicited an increase in antioxidant capacity suggesting resource reallocation from signalling to redox homeostasis. Carotenoids counteracted the effect of oxidative challenge on lipophilic (but not hydrophilic) antioxidant capacity, thereby supporting carotenoid antioxidant function in vivo. This is inconsistent with hypotheses proposing that signalling honesty is maintained through either ROS-induced carotenoid degradation or the pro-oxidant effect of high levels of carotenoid-cleavage products acting as a physiological handicap. Our data further suggest that assessment of lipophilic antioxidant capacity is necessary to fully understand the role of redox processes in ecology and evolution.

  10. Opposing effects of oxidative challenge and carotenoids on antioxidant status and condition-dependent sexual signalling

    PubMed Central

    Tomášek, Oldřich; Gabrielová, Barbora; Kačer, Petr; Maršík, Petr; Svobodová, Jana; Syslová, Kamila; Vinkler, Michal; Albrecht, Tomáš

    2016-01-01

    Several recent hypotheses consider oxidative stress to be a primary constraint ensuring honesty of condition-dependent carotenoid-based signalling. The key testable difference between these hypotheses is the assumed importance of carotenoids for redox homeostasis, with carotenoids being either antioxidant, pro-oxidant or unimportant. We tested the role of carotenoids in redox balance and sexual signalling by exposing adult male zebra finches (Taeniopygia guttata) to oxidative challenge (diquat dibromide) and manipulating carotenoid intake. As the current controversy over the importance of carotenoids as antioxidants could stem from the hydrophilic basis of commonly-used antioxidant assays, we used the novel measure of in vivo lipophilic antioxidant capacity. Oxidative challenge reduced beak pigmentation but elicited an increase in antioxidant capacity suggesting resource reallocation from signalling to redox homeostasis. Carotenoids counteracted the effect of oxidative challenge on lipophilic (but not hydrophilic) antioxidant capacity, thereby supporting carotenoid antioxidant function in vivo. This is inconsistent with hypotheses proposing that signalling honesty is maintained through either ROS-induced carotenoid degradation or the pro-oxidant effect of high levels of carotenoid-cleavage products acting as a physiological handicap. Our data further suggest that assessment of lipophilic antioxidant capacity is necessary to fully understand the role of redox processes in ecology and evolution. PMID:27000655

  11. The oxidative costs of reproduction are group-size dependent in a wild cooperative breeder.

    PubMed

    Cram, Dominic L; Blount, Jonathan D; Young, Andrew J

    2015-11-22

    Life-history theory assumes that reproduction entails a cost, and research on cooperatively breeding societies suggests that the cooperative sharing of workloads can reduce this cost. However, the physiological mechanisms that underpin both the costs of reproduction and the benefits of cooperation remain poorly understood. It has been hypothesized that reproductive costs may arise in part from oxidative stress, as reproductive investment may elevate exposure to reactive oxygen species, compromising survival and future reproduction and accelerating senescence. However, experimental evidence of oxidative costs of reproduction in the wild remains scarce. Here, we use a clutch-removal experiment to investigate the oxidative costs of reproduction in a wild cooperatively breeding bird, the white-browed sparrow weaver, Plocepasser mahali. Our results reveal costs of reproduction that are dependent on group size: relative to individuals in groups whose eggs were experimentally removed, individuals in groups that raised offspring experienced an associated cost (elevated oxidative damage and reduced body mass), but only if they were in small groups containing fewer or no helpers. Furthermore, during nestling provisioning, individuals that provisioned at higher rates showed greater within-individual declines in body mass and antioxidant protection. Our results provide rare experimental evidence that reproduction can negatively impact both oxidative status and body mass in the wild, and suggest that these costs can be mitigated in cooperative societies by the presence of additional helpers. These findings have implications for our understanding of the energetic and oxidative costs of reproduction, and the benefits of cooperation in animal societies.

  12. Molecular orientation dependence of hole-injection barrier in pentacene thin film on the Au surface in organic thin film transistor

    NASA Astrophysics Data System (ADS)

    Ihm, Kyuwook; Kim, Bongsoo; Kang, Tai-Hee; Kim, Ki-Jeong; Joo, Min Ho; Kim, Tae Hyeong; Yoon, Sang Soo; Chung, Sukmin

    2006-07-01

    We have investigated the effects of a buffer layer insertion on the performance of the pentacene based thin film transistor with a bottom contact structure. When the pentacene molecules have a standing up coordination on the Au surface that is modified by the benzenethiol or methanethiol, the transition region in the pentacene thin film is removed along the boundary between the Au and silicon oxide region, and the hole-injection barrier decreases by 0.4eV. Pentacene on various surfaces showed that the highly occupied molecular level is 0.2-0.4eV lower in the standing up coordination than in the lying down coordination.

  13. Role of nitric oxide synthases in early blood-brain barrier disruption following transient focal cerebral ischemia.

    PubMed

    Jiang, Zheng; Li, Chun; Arrick, Denise M; Yang, Shu; Baluna, Alexandra E; Sun, Hong

    2014-01-01

    The role of nitric oxide synthases (NOSs) in early blood-brain barrier (BBB) disruption was determined using a new mouse model of transient focal cerebral ischemia. Ischemia was induced by ligating the middle cerebral artery (MCA) at its M2 segment and reperfusion was induced by releasing the ligation. The diameter alteration of the MCA, arterial anastomoses and collateral arteries were imaged and measured in real time. BBB disruption was assessed by Evans Blue (EB) and sodium fluorescein (Na-F) extravasation at 3 hours of reperfusion. The reperfusion produced an extensive vasodilation and a sustained hyperemia. Although expression of NOSs was not altered at 3 hours of reperfusion, L-NAME (a non-specific NOS inhibitor) abolished reperfusion-induced vasodilation/hyperemia and significantly reduced EB and Na-F extravasation. L-NIO (an endothelial NOS (eNOS) inhibitor) significantly attenuated cerebral vasodilation but not BBB disruption, whereas L-NPA and 7-NI (neuronal NOS (nNOS) inhibitors) significantly reduced BBB disruption but not cerebral vasodilation. In contrast, aminoguanidine (AG) (an inducible NOS (iNOS) inhibitor) had less effect on either cerebral vasodilation or BBB disruption. On the other hand, papaverine (PV) not only increased the vasodilation/hyperemia but also significantly reduced BBB disruption. Combined treatment with L-NAME and PV preserved the vasodilation/hyperemia and significantly reduced BBB disruption. Our findings suggest that nNOS may play a major role in early BBB disruption following transient focal cerebral ischemia via a hyperemia-independent mechanism.

  14. Eltrombopag, a thrombopoietin mimetic, crosses the blood-brain barrier and impairs iron-dependent hippocampal neuron dendrite development.

    PubMed

    Bastian, T W; Duck, K A; Michalopoulos, G C; Chen, M J; Liu, Z-J; Connor, J R; Lanier, L M; Sola-Visner, M C; Georgieff, M K

    2017-03-01

    Essentials Potential neurodevelopmental side effects of thrombopoietin mimetics need to be considered. The effects of eltrombopag (ELT) on neuronal iron status and dendrite development were assessed. ELT crosses the blood-brain barrier and causes iron deficiency in developing neurons. ELT blunts dendrite maturation, indicating a need for more safety studies before neonatal use.

  15. Cortactin deficiency causes increased RhoA/ROCK1-dependent actomyosin contractility, intestinal epithelial barrier dysfunction, and disproportionately severe DSS-induced colitis.

    PubMed

    Citalán-Madrid, A F; Vargas-Robles, H; García-Ponce, A; Shibayama, M; Betanzos, A; Nava, P; Salinas-Lara, C; Rottner, K; Mennigen, R; Schnoor, M

    2017-01-25

    The intestinal epithelium constitutes a first line of defense of the innate immune system. Epithelial dysfunction is a hallmark of intestinal disorders such as inflammatory bowel diseases (IBDs). The actin cytoskeleton controls epithelial barrier integrity but the function of actin regulators such as cortactin is poorly understood. Given that cortactin controls endothelial permeability, we hypothesized that cortactin is also important for epithelial barrier regulation. We found increased permeability in the colon of cortactin-KO mice that was accompanied by reduced levels of ZO-1, claudin-1, and E-cadherin. By contrast, claudin-2 was upregulated. Cortactin deficiency increased RhoA/ROCK1-dependent actomyosin contractility, and inhibition of ROCK1 rescued the barrier defect. Interestingly, cortactin deficiency caused increased epithelial proliferation without affecting apoptosis. KO mice did not develop spontaneous colitis, but were more susceptible to dextran sulfate sodium colitis and showed severe colon tissue damage and edema formation. KO mice with colitis displayed strong mucus deposition and goblet cell depletion. In healthy human colon tissues, cortactin co-localized with ZO-1 at epithelial cell contacts. In IBDs patients, we observed decreased cortactin levels and loss of co-localization with ZO-1. Thus, cortactin is a master regulator of intestinal epithelial barrier integrity in vivo and could serve as a suitable target for pharmacological intervention in IBDs.Mucosal Immunology advance online publication, 25 January 2017; doi:10.1038/mi.2016.136.

  16. Oxidative stress and inflammatory markers are associated with depression and nicotine dependence.

    PubMed

    Vargas, Heber Odebrecht; Nunes, Sandra Odebrecht Vargas; de Castro, Márcia Regina Pizzo; Vargas, Mateus Mendonça; Barbosa, Décio Sabbatini; Bortolasci, Chiara Cristina; Venugopal, Kamalesh; Dodd, Seetal; Berk, Michael

    2013-06-07

    To determine if oxidative stress and inflammation are linked with major depressive disorder, nicotine dependence and both disorders combined. This study comprised 150 smokers and 191 never smokers. The instruments were: a socio-demographic questionnaire, diagnoses of mood disorder and nicotine dependence according to DSM-IV, (SCID-IV), and the Alcohol, Smoking and Substance Involvement Screening Test. Laboratory assessments included: nitric oxide metabolites (NOx), lipid hydroperoxides, malondialdehyde (MDA), total reactive antioxidant potential (TRAP), advanced oxidation protein products (AOPP), fibrinogen concentrations, homocysteine, erythrocytes sedimentation rate (ESR) and high-sensitivity C-reactive protein (hs-CRP) were assayed from blood specimens. Statistically significant differences were found among depressed smokers who had more severe depressive symptoms, a higher risk of alcohol consumption, more suicide attempts, and more disability for work than non-depressed never smokers. Depressed smokers had significantly higher levels of NOx, fibrinogen, hs-CRP, AOPP, ESR and lower levels of TRAP compared to non-depressed never smokers. Depressed smokers had significant levels of oxidative stress and inflammatory biomarkers after adjusting for gender, age, years of education, disability for work, and laboratory measures. The levels of NOx, lipid hydroperoxides, AOPP, and fibrinogen were substantially higher, whereas levels of TRAP were lower in depressed smokers compared to non-depressed never smokers. (1) Depressed smokers exhibited altered concentrations of NOx, lipid hydroperoxides, AOPP, TRAP, and fibrinogen. (2) Depressed smokers were more unable to work, showed more severe depressive symptoms and attempted suicide more frequently.

  17. Anomalous quantum efficiency for photoconduction and its power dependence in metal oxide semiconductor nanowires

    NASA Astrophysics Data System (ADS)

    Chen, R. S.; Wang, W. C.; Lu, M. L.; Chen, Y. F.; Lin, H. C.; Chen, K. H.; Chen, L. C.

    2013-07-01

    The quantum efficiency and carrier lifetime that decide the photoconduction (PC) efficiencies in the metal oxide semiconductor nanowires (NWs) have been investigated. The experimental result surprisingly shows that the SnO2, TiO2, WO3, and ZnO NWs reveal extraordinary quantum efficiencies in common, which are over one to three orders of magnitude lower than the theoretical expectation. The surface depletion region (SDR)-controlled photoconductivity is proposed to explain the anomalous quantum efficiency and its power dependence. The inherent difference between the metal oxide nanostructures such as carrier lifetime, carrier concentration, and dielectric constant leading to the distinct PC performance and behavior are also discussed.The quantum efficiency and carrier lifetime that decide the photoconduction (PC) efficiencies in the metal oxide semiconductor nanowires (NWs) have been investigated. The experimental result surprisingly shows that the SnO2, TiO2, WO3, and ZnO NWs reveal extraordinary quantum efficiencies in common, which are over one to three orders of magnitude lower than the theoretical expectation. The surface depletion region (SDR)-controlled photoconductivity is proposed to explain the anomalous quantum efficiency and its power dependence. The inherent difference between the metal oxide nanostructures such as carrier lifetime, carrier concentration, and dielectric constant leading to the distinct PC performance and behavior are also discussed. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01635h

  18. Overexpression of endothelial nitric oxide synthase improves endothelium-dependent vasodilation in arteries infused with helper-dependent adenovirus.

    PubMed

    Jiang, Bo; Du, Liang; Flynn, Rowan; Dronadula, Nagadhara; Zhang, Jingwan; Kim, Francis; Dichek, David

    2012-11-01

    Adenoviral vectors (Ad) are useful tools for in vivo gene transfer into endothelial cells. However, endothelium-dependent vasodilation is impaired after Ad infusion, and this impairment is not prevented by use of advanced-generation "helper-dependent" (HD) Ad that lack all viral genes. We hypothesized that endothelium-dependent vasodilation could be improved in Ad-infused arteries by overexpression of endothelial nitric oxide synthase (eNOS). We tested this hypothesis in hyperlipidemic, atherosclerosis-prone rabbits because HDAd will likely be used for treating and preventing atherosclerosis. Moreover, the consequences of eNOS overexpression might differ in normal and atherosclerosis-prone arteries and could include atherogenic effects, as reported in transgenic mice. We cloned rabbit eNOS and constructed an HDAd that expresses it. HDAdeNOS increased NO production by cultured endothelial cells and increased arterial eNOS mRNA in vivo by ∼10-fold. Compared to arteries infused with a control HDAd, HDAdeNOS-infused arteries of hyperlipidemic rabbits had significantly improved endothelium-dependent vasodilation, and similar responses to phenylephrine and nitroprusside. Moreover, infusion of HDAdeNOS had local atheroprotective effects including large, significant decreases in intimal lipid accumulation and arterial tumor necrosis factor (TNF)-α expression (p≤0.04 for both). HDAdeNOS infusion yields a durable (≥2 weeks) increase in arterial eNOS expression, improves vasomotor function, and reduces artery wall inflammation and lipid accumulation. Addition of an eNOS expression cassette improves the performance of HDAd, has no harmful effects, and may reduce atherosclerotic lesion growth.

  19. Efficient spin injection through a crystalline AlOx tunnel barrier prepared by the oxidation of an ultra-thin Al epitaxial layer on GaAs

    NASA Astrophysics Data System (ADS)

    Nishizawa, N.; Munekata, H.

    2013-07-01

    We report that an ultra-thin, post-oxidized aluminum epilayer grown on the AlGaAs surface works as a high-quality tunnel barrier for spin injection from a ferromagnetic metal to a semiconductor. One of the key points of the present oxidation method is the formation of the crystalline AlOx template layer without oxidizing the AlGaAs region near the Al/AlGaAs interface. The oxidized Al layer is not amorphous but show well-defined single crystalline feature reminiscent of the spinel γ-AlOx phase. A spin-light emitting diode consisting of a Fe layer, a crystalline AlOx barrier layer, and an AlGaAs-InGaAs double hetero-structure has exhibited circularly polarized electroluminescence with circular polarization of PEL ˜ 0.145 at the remnant magnetization state of the Fe layer, indicating the relatively high spin injection efficiency (≡2PEL/PFe) of 0.63.

  20. Oral atorvastatin therapy increases nitric oxide-dependent cutaneous vasodilation in humans by decreasing ascorbate-sensitive oxidants.

    PubMed

    Holowatz, Lacy A; Kenney, W Larry

    2011-09-01

    Elevated low-density lipoproteins (LDL) are associated with cutaneous microvascular dysfunction partially mediated by increased arginase activity, which is decreased following a systemic atorvastatin therapy. We hypothesized that increased ascorbate-sensitive oxidant stress, partially mediated through uncoupled nitric oxide synthase (NOS) induced by upregulated arginase, contributes to cutaneous microvascular dysfunction in hypercholesterolemic (HC) humans. Four microdialysis fibers were placed in the skin of nine HC (LDL = 177 ± 6 mg/dl) men and women before and after 3 mo of a systemic atorvastatin intervention and at baseline in nine normocholesterolemic (NC) (LDL = 95 ± 4 mg/dl) subjects. Sites served as control, NOS inhibited, L-ascorbate, and arginase-inhibited+L-ascorbate. Skin blood flow was measured while local skin heating (42°C) induced NO-dependent vasodilation. After the established plateau in all sites, 20 mM ≪ngname≫ was infused to quantify NO-dependent vasodilation. Data were normalized to maximum cutaneous vascular conductance (CVC) (sodium nitroprusside + 43°C). The plateau in vasodilation during local heating (HC: 78 ± 4 vs. NC: 96 ± 2% CVC(max), P < 0.01) and NO-dependent vasodilation (HC: 40 ± 4 vs. NC: 54 ± 4% CVC(max), P < 0.01) was reduced in the HC group. Acute L-ascorbate alone (91 ± 5% CVC(max), P < 0.001) or combined with arginase inhibition (96 ± 3% CVC(max), P < 0.001) augmented the plateau in vasodilation in the HC group but not the NC group (ascorbate: 96 ± 2; combo: 93 ± 4% CVC(max), both P > 0.05). After the atorvastatin intervention NO-dependent vasodilation was augmented in the HC group (HC postatorvastatin: 64 ± 4% CVC(max), P < 0.01), and there was no further effect of ascorbate alone (58 ± 4% CVC(max,) P > 0.05) or combined with arginase inhibition (67 ± 4% CVC(max,) P > 0.05). Increased ascorbate-sensitive oxidants contribute to hypercholesteromic associated cutaneous microvascular dysfunction which is

  1. Energy dependence of the trapping of uranium atoms by aluminum oxide surfaces

    NASA Technical Reports Server (NTRS)

    Librecht, K. G.

    1979-01-01

    The energy dependence of the trapping probability for sputtered U-235 atoms striking an oxidized aluminum collector surface at energies between 1 eV and 184 eV was measured. At the lowest energies, approximately 10% of the uranium atoms are not trapped, while above 10 eV essentially all of them stick. Trapping probabilities averaged over the sputtered energy distribution for uranium incident on gold and mica are also presented.

  2. Thermoelectric properties of nano-granular indium-tin-oxide within modified electron filtering model with chemisorption-type potential barriers

    NASA Astrophysics Data System (ADS)

    Brinzari, V.; Nika, D. L.; Damaskin, I.; Cho, B. K.; Korotcenkov, G.

    2016-07-01

    In this work, an approach to the numerical study of the thermoelectric parameters of nanoscale indium tin oxide (ITO, Sn content<10 at%) based on an electron filtering model (EFM) was developed. Potential barriers at grain boundaries were assumed to be responsible for a filtering effect. In the case of the dominant inelastic scattering of electrons, the maximal distance between potential barriers was limited in this modified model. The algorithm for such characteristic length calculation was proposed, and its value was evaluated for ITO. In addition, the contributions of different scattering mechanisms (SMs) in electron transport were examined. It was confirmed that in bulk ITO, the scattering on polar optical phonons (POPs) and ionized impurities dominates, limiting electron transport. In the framework of the filtering model, the basic thermoelectric parameters (i.e., electrical conductivity, mobility, Seebeck coefficient, and power factor (PF)) were calculated for ITO in the temperature range of 100-500 °C as a function of potential barrier height. The results demonstrated a sufficient rise of the Seebeck coefficient with an increase in barrier height and specific behavior of PF. It was found that PF is very sensitive to barrier height, and at its optimal value for granular ITO, it may exceed the PF for bulk ITO by 3-5 times. The PF maximum was achieved by band bending, slightly exceeding Fermi energy. The nature of surface potential barriers in nano-granular ITO with specific grains is due to the oxygen chemisorption effect, and this can be observed despite of the degeneracy of the conduction band (CB). This hypothesis and the corresponding calculations are in good agreement with recent experimental studies [Brinzari et al. Thin Solid Films 552 (2014) 225].

  3. Urolithins display both antioxidant and pro-oxidant activities depending on assay system and conditions.

    PubMed

    Kallio, Tuija; Kallio, Johanna; Jaakkola, Mari; Mäki, Marianne; Kilpeläinen, Pekka; Virtanen, Vesa

    2013-11-13

    The biological effects of polyphenolic ellagitannins are mediated by their intestinal metabolites, urolithins. This study investigated redox properties of urolithins A and B using ORAC assay, three cell-based assays, copper-initiated pro-oxidant activity (CIPA) assay, and cyclic voltammetry. Urolithins were strong antioxidants in the ORAC assay, but mostly pro-oxidants in cell-based assays, although urolithin A was an antioxidant in cell culture medium. Parent compound ellagic acid was a strong extracellular antioxidant, but showed no response in the intracellular assay. The CIPA assay confirmed the pro-oxidant activity of ellagitannin metabolites. In the cell proliferation assay, urolithins but not ellagic acid decreased growth and metabolism of HepG2 liver cells. In cyclic voltammetry, the oxidation of urolithin A was partly reversible, but that of urolithin B was irreversible. These results illustrate how strongly measured redox properties depend on the employed assay system and conditions and emphasize the importance of studying pro-oxidant and antioxidant activities in parallel.

  4. Salinity-dependent nickel accumulation and oxidative stress responses in the euryhaline killifish (Fundulus heteroclitus).

    PubMed

    Blewett, Tamzin A; Wood, Chris M

    2015-02-01

    The mechanisms of nickel (Ni) toxicity in marine fish remain unclear, although evidence from freshwater (FW) fish suggests that Ni can act as a pro-oxidant. This study investigated the oxidative stress effects of Ni on the euryhaline killifish (Fundulus heteroclitus) as a function of salinity. Killifish were exposed to sublethal levels (5, 10, and 20 mg L(-1)) of waterborne Ni for 96 h in FW (0 ppt) and 100 % saltwater (SW) (35 ppt). In general, SW was protective against both Ni accumulation and indicators of oxidative stress [protein carbonyl formation and catalase (CAT) activity]. This effect was most pronounced at the highest Ni exposure level. For example, FW intestine showed increased Ni accumulation relative to SW intestine at 20 mg Ni L(-1), and this was accompanied by significantly greater protein carbonylation and CAT activity in this tissue. There were exceptions, however, in that although liver of FW killifish at the highest exposure concentration showed greater Ni accumulation relative to SW liver, levels of CAT activity were greatly decreased. This may relate to tissue- and salinity-specific differences in oxidative stress responses. The results of the present study suggest (1) that there was Ni-induced oxidative stress in killifish, (2) that the effects of salinity depend on differences in the physiology of the fish in FW versus SW, and (3) that increased levels of cations (sodium, calcium, potassium, and magnesium) and anions (SO4 and Cl) in SW are likely protective against Ni accumulation in tissues exposed to the aquatic environment.

  5. The red-vine-leaf extract AS195 increases nitric oxide synthase-dependent nitric oxide generation and decreases oxidative stress in endothelial and red blood cells.

    PubMed

    Grau, Marijke; Bölck, Birgit; Bizjak, Daniel Alexander; Stabenow, Christina Julia Annika; Bloch, Wilhelm

    2016-02-01

    The red-vine-leaf extract AS195 improves cutaneous oxygen supply and the microcirculation in patients suffering from chronic venous insufficiency. Regulation of blood flow was associated to nitric oxide synthase (NOS)-dependent NO (nitric oxide) production, and endothelial and red blood cells (RBC) have been shown to possess respective NOS isoforms. It was hypothesized that AS195 positively affects NOS activation in human umbilical vein endothelial cells (HUVECs) and RBC. Because patients with microvascular disorders show increased oxidative stress which limits NO bioavailability, it was further hypothesized that AS195 increases NO bioavailability by decreasing the content of reactive oxygen species (ROS) and increasing antioxidant capacity. Cultured HUVECs and RBCs from healthy volunteers were incubated with AS195 (100 μmol/L), tert-butylhydroperoxide (TBHP, 1 mmol/L) to induce oxidative stress and with both AS195 and TBHP. Endothelial and red blood cell-nitric oxide synthase (RBC-NOS) activation significantly increased after AS195 incubation. Nitrite concentration, a marker for NO production, increased in HUVEC but decreased in RBC after AS195 application possibly due to nitrite scavenging potential of flavonoids. S-nitrosylation of RBC cytoskeletal spectrins and RBC deformability were increased after AS195 incubation. TBHP-induced ROS were decreased by AS195, and antioxidative capacity was significantly increased in AS195-treated cells. TBHP also reduced RBC deformability, but reduction was attenuated by parallel incubation with AS195. Adhesion of HUVEC was also reduced after AS195 treatment. Red-vine-leaf extract AS195 increases NOS activation and decreases oxidative stress. Both mechanisms increase NO bioavailability, improve cell function, and may thus account for enhanced microcirculation in both health and disease.

  6. Oxidative Burst-Dependent NETosis Is Implicated in the Resolution of Necrosis-Associated Sterile Inflammation.

    PubMed

    Biermann, Mona H C; Podolska, Malgorzata J; Knopf, Jasmin; Reinwald, Christiane; Weidner, Daniela; Maueröder, Christian; Hahn, Jonas; Kienhöfer, Deborah; Barras, Alexandre; Boukherroub, Rabah; Szunerits, Sabine; Bilyy, Rostyslav; Hoffmann, Markus; Zhao, Yi; Schett, Georg; Herrmann, Martin; Munoz, Luis E

    2016-01-01

    Necrosis is associated with a profound inflammatory response. The regulation of necrosis-associated inflammation, particularly the mechanisms responsible for resolution of inflammation is incompletely characterized. Nanoparticles are known to induce plasma membrane damage and necrosis followed by sterile inflammation. We observed that injection of metabolically inert nanodiamonds resulted in paw edema in WT and Ncf1** mice. However, while inflammation quickly resolved in WT mice, it persisted over several weeks in Ncf1** mice indicating failure of resolution of inflammation. Mechanistically, NOX2-dependent reactive oxygen species (ROS) production and formation of neutrophil extracellular traps were essential for the resolution of necrosis-induced inflammation: hence, by evaluating the fate of the particles at the site of inflammation, we observed that Ncf1** mice deficient in NADPH-dependent ROS failed to generate granulation tissue therefore being unable to trap the nanodiamonds. These data suggest that NOX2-dependent NETosis is crucial for preventing the chronification of the inflammatory response to tissue necrosis by forming NETosis-dependent barriers between the necrotic and healthy surrounding tissue.

  7. Oxidative Burst-Dependent NETosis Is Implicated in the Resolution of Necrosis-Associated Sterile Inflammation

    PubMed Central

    Biermann, Mona H. C.; Podolska, Malgorzata J.; Knopf, Jasmin; Reinwald, Christiane; Weidner, Daniela; Maueröder, Christian; Hahn, Jonas; Kienhöfer, Deborah; Barras, Alexandre; Boukherroub, Rabah; Szunerits, Sabine; Bilyy, Rostyslav; Hoffmann, Markus; Zhao, Yi; Schett, Georg; Herrmann, Martin; Munoz, Luis E.

    2016-01-01

    Necrosis is associated with a profound inflammatory response. The regulation of necrosis-associated inflammation, particularly the mechanisms responsible for resolution of inflammation is incompletely characterized. Nanoparticles are known to induce plasma membrane damage and necrosis followed by sterile inflammation. We observed that injection of metabolically inert nanodiamonds resulted in paw edema in WT and Ncf1** mice. However, while inflammation quickly resolved in WT mice, it persisted over several weeks in Ncf1** mice indicating failure of resolution of inflammation. Mechanistically, NOX2-dependent reactive oxygen species (ROS) production and formation of neutrophil extracellular traps were essential for the resolution of necrosis-induced inflammation: hence, by evaluating the fate of the particles at the site of inflammation, we observed that Ncf1** mice deficient in NADPH-dependent ROS failed to generate granulation tissue therefore being unable to trap the nanodiamonds. These data suggest that NOX2-dependent NETosis is crucial for preventing the chronification of the inflammatory response to tissue necrosis by forming NETosis-dependent barriers between the necrotic and healthy surrounding tissue. PMID:27990145

  8. MgGa2O4 spinel barrier for magnetic tunnel junctions: Coherent tunneling and low barrier height

    NASA Astrophysics Data System (ADS)

    Sukegawa, Hiroaki; Kato, Yushi; Belmoubarik, Mohamed; Cheng, P.-H.; Daibou, Tadaomi; Shimomura, Naoharu; Kamiguchi, Yuuzo; Ito, Junichi; Yoda, Hiroaki; Ohkubo, Tadakatsu; Mitani, Seiji; Hono, Kazuhiro

    2017-03-01

    Epitaxial Fe/magnesium gallium spinel oxide (MgGa2O4)/Fe(001) magnetic tunnel junctions (MTJs) were fabricated by magnetron sputtering. A tunnel magnetoresistance (TMR) ratio up to 121% at room temperature (196% at 4 K) was observed, suggesting a TMR enhancement by the coherent tunneling effect in the MgGa2O4 barrier. The MgGa2O4 layer had a spinel structure and it showed good lattice matching with the Fe layers owing to slight tetragonal lattice distortion of MgGa2O4. Barrier thickness dependence of the tunneling resistance and current-voltage characteristics revealed that the height of the MgGa2O4 barrier is much lower than that of an MgAl2O4 barrier. This study demonstrates the potential of Ga-based spinel oxides for MTJ barriers having a large TMR ratio at a low resistance area product.

  9. Cigarette smoke causes lung vascular barrier dysfunction via oxidative stress-mediated inhibition of RhoA and focal adhesion kinase

    PubMed Central

    Sakhatskyy, Pavlo; Grinnell, Katie; Newton, Julie; Ortiz, Melanie; Wang, Yulian; Sanchez-Esteban, Juan; Harrington, Elizabeth O.; Rounds, Sharon

    2011-01-01

    Cigarette smoke (CS) is a major cause of chronic lung and cardiovascular diseases. Recent studies indicate that tobacco use is also a risk factor for acute lung injury (ALI) associated with blunt trauma. Increased endothelial cell (EC) permeability is a hallmark of ALI. CS increases EC permeability in vitro and in vivo; however, the underlying mechanism is not well understood. In this study, we found that only 6 h of exposure to CS impaired endothelial barrier function in vivo, an effect associated with increased oxidative stress in the lungs and attenuated by the antioxidant N-acetylcysteine (NAC). CS also exacerbated lipopolysaccharide (LPS)-induced increase in vascular permeability in vivo. Similar additive effects were also seen in cultured lung EC exposed to cigarette smoke extract (CSE) and LPS. We further demonstrated that CSE caused disruption of focal adhesion complexes (FAC), F-actin fibers, and adherens junctions (AJ) and decreased activities of RhoA and focal adhesion kinase (FAK) in cultured lung EC. CSE-induced inhibition of RhoA and FAK, endothelial barrier dysfunction, and disassembly of FAC, F-actin, and AJ were prevented by NAC. In addition, the deleterious effects of CSE on FAC, F-actin fibers, and AJ were blunted by overexpression of constitutively active RhoA and of FAK. Our data indicate that CS causes endothelial barrier dysfunction via oxidative stress-mediated inhibition of RhoA and FAK. PMID:21984567

  10. Furnace Cyclic Behavior of Plasma-Sprayed Zirconia-Yttria and Multi-Component Rare Earth Oxide Doped Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Nesbitt, James A.; McCue, Terry R.; Barrett, Charles A.; Miller, Robert A.

    2002-01-01

    Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to enable further increases in engine temperatures. However, the coating performance and durability become a major concern under the increasingly harsh thermal cycling conditions. Advanced zirconia- and hafnia-based cluster oxide thermal barrier coatings with lower thermal conductivity and improved thermal stability are being developed using a high-heat-flux laser-rig based test approach. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of numerous candidate coating materials was carried out using conventional furnace cyclic tests. In this paper, furnace thermal cyclic behavior of the advanced plasma-sprayed zirconia-yttria-based thermal barrier coatings that were co-doped with multi-component rare earth oxides was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied by using scanning electron microscopy combined with X-ray diffraction phase analysis after the furnace tests. The coating cyclic lifetime will be discussed in relation to coating phase structures, total dopant concentrations, and other properties.

  11. The temperature dependence of intersubband absorption in a barrier-doped GaAs/Al 0.3Ga 0.7As quantum well structure

    NASA Astrophysics Data System (ADS)

    Szmulowicz, F.; Manasreh, M. O.; Fischer, D. W.; Madarasz, F.; Evans, K. R.; Stutz, E.; Vaughan, T.

    We compare the results of an envelope function (EFA) calculation of absorption spectra as a function of temperature of a barrier-doped GaAs/Al 0.3Ga 0.7As multiple quantum well (MQW) with experimental results. The linewidth, total integrated area, and peak positions of the intersubband transition (IT) in the MQW were measured as a function of temperature with the infrared absorption technique. We infer the density of electrons σ in the well from the total integrated intensity of the IT. Using the temperature dependence of σ we find that the Fermi energy in our MQW is also temperature dependent. The peak position of the IT is found to exhibit a nonlinear blue shift as the temperature is lowered. We calculate a one-electron energy band structure of the MQW versus the in-plane wave vector as a function of temperature using Ekenberg's nonparabolic-anisotropic EFA formalism. In our calculation we employ temperature dependent effective masses in both the well and barrier materials and temperature dependent conduction band offset and nonparabolicity parameter. Using the calculated bands and Fermi distribution functions to reflect the occupancies of both the ground and excited states with temperature dependent Fermi levels, we also obtain the optical absorption spectra as a function of temperature. These "raw" calculated spectra are then convoluted with a Lorentzian broadening function using the broadening parameters obtained from the measured lineshapes. The peak of the broadened spectra shows hardly any shift as a function of temperature. We conclude that the exchange interaction for the ground state electrons, which is temperature dependent owing to the temperature dependence of σ, is responsible for the observed peak positions as well as for their blue shift.

  12. Concentration dependent effect of calcium on brain mitochondrial bioenergetics and oxidative stress parameters

    PubMed Central

    Pandya, Jignesh D.; Nukala, Vidya N.; Sullivan, Patrick G.

    2013-01-01

    Mitochondrial dysfunction following traumatic brain and spinal cord injury (TBI and SCI) plays a pivotal role in the development of secondary pathophysiology and subsequent neuronal cell death. Previously, we demonstrated a loss of mitochondrial bioenergetics in the first 24 h following TBI and SCI initiates a rapid and extensive necrotic event at the primary site of injury. Within the mitochondrial derived mechanisms, the cross talk and imbalance amongst the processes of excitotoxicity, Ca2+ cycling/overload, ATP synthesis, free radical production and oxidative damage ultimately lead to mitochondrial damage followed by neuronal cell death. Mitochondria are one of the important organelles that regulate intracellular calcium (Ca2+) homeostasis and are equipped with a tightly regulated Ca2+ transport system. However, owing to the lack of consensus and the link between downstream effects of calcium in published literature, we undertook a systematic in vitro study for measuring concentration dependent effects of calcium (100–1000 nmols/mg mitochondrial protein) on mitochondrial respiration, enzyme activities, reactive oxygen/nitrogen species (ROS/RNS) generation, membrane potential (ΔΨ) and oxidative damage markers in isolated brain mitochondria. We observed a dose- and time-dependent inhibition of mitochondrial respiration by calcium without influencing mitochondrial pyruvate dehydrogenase complex (PDHC) and NADH dehydrogenase (Complex I) enzyme activities. We observed dose-dependent decreased production of hydrogen peroxide and total ROS/RNS species generation by calcium and no significant changes in protein and lipid oxidative damage markers. These results may shed new light on the prevailing dogma of the direct effects of calcium on mitochondrial bioenergetics, free radical production and oxidative stress parameters that are primary regulatory mitochondrial mechanisms following neuronal injury. PMID:24385963

  13. Genome-enabled studies of anaerobic, nitrate-dependent iron oxidation in the chemolithoautotrophic bacterium Thiobacillus denitrificans

    PubMed Central

    Beller, Harry R.; Zhou, Peng; Legler, Tina C.; Chakicherla, Anu; Kane, Staci; Letain, Tracy E.; A. O’Day, Peggy

    2013-01-01

    Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV) oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II) oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II)-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II) oxidation, namely (a) whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV) oxides as electron donors under denitrifying conditions], (b) Fe(II) oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c) random transposon-mutagenesis studies with screening for Fe(II) oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II) oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III), which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II) oxidation and to current concepts of reverse electron transfer. A transposon mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I) was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II) oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV) oxidation, nor have other c-type cytochromes yet been implicated in the process. PMID:24065960

  14. Anaerobic Oxidization of Methane in a Minerotrophic Peatland: Enrichment of Nitrite-Dependent Methane-Oxidizing Bacteria

    PubMed Central

    Zhu, Baoli; van Dijk, Gijs; Fritz, Christian; Smolders, Alfons J. P.; Pol, Arjan; Jetten, Mike S. M.

    2012-01-01

    The importance of anaerobic oxidation of methane (AOM) as a methane sink in freshwater systems is largely unexplored, particularly in peat ecosystems. Nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and reported to be catalyzed by the bacterium “Candidatus Methylomirabilis oxyfera,” which is affiliated with the NC10 phylum. So far, several “Ca. Methylomirabilis oxyfera” enrichment cultures have been obtained using a limited number of freshwater sediments or wastewater treatment sludge as the inoculum. In this study, using stable isotope measurements and porewater profiles, we investigated the potential of n-damo in a minerotrophic peatland in the south of the Netherlands that is infiltrated by nitrate-rich ground water. Methane and nitrate profiles suggested that all methane produced was oxidized before reaching the oxic layer, and NC10 bacteria could be active in the transition zone where countergradients of methane and nitrate occur. Quantitative PCR showed high NC10 bacterial cell numbers at this methane-nitrate transition zone. This soil section was used to enrich the prevalent NC10 bacteria in a continuous culture supplied with methane and nitrite at an in situ pH of 6.2. An enrichment of nitrite-reducing methanotrophic NC10 bacteria was successfully obtained. Phylogenetic analysis of retrieved 16S rRNA and pmoA genes showed that the enriched bacteria were very similar to the ones found in situ and constituted a new branch of NC10 bacteria with an identity of less than 96 and 90% to the 16S rRNA and pmoA genes of “Ca. Methylomirabilis oxyfera,” respectively. The results of this study expand our knowledge of the diversity and distribution of NC10 bacteria in the environment and highlight their potential contribution to nitrogen and methane cycles. PMID:23042166

  15. Anodization control for barrier-oxide thinning and 3D interconnected pores and direct electrodeposition of nanowire networks on native aluminium substrates.

    PubMed

    Gillette, Eleanor; Wittenberg, Stefanie; Graham, Lauren; Lee, Kwijong; Rubloff, Gary; Banerjee, Parag; Lee, Sang Bok

    2015-02-07

    Here we report a strategy for combining techniques for pore branching and barrier layer thinning to produce 3D porous anodized aluminum oxide films with direct ohmic contact to the native aluminum. This method provides an example of a rationally designed template which need not be removed from the aluminum, but which is also not constrained to traditional 2D pore geometry. We first demonstrate the barrier layer removal and pore branching techniques independently, and then combine them to produce free standing arrays of interconnected Ni nanostructures. Nickel nanostructures are deposited directly onto the aluminum to demonstrate the success of the structural modification, and showcase the potential for these films to be used as templates. This approach is the first to demonstrate the design and execution of multiple pore modification techniques in the same membrane, and demonstrates the first directly deposited 3D structures on aluminum substrates.

  16. Toxic Effects of Maternal Zearalenone Exposure on Intestinal Oxidative Stress, Barrier Function, Immunological and Morphological Changes in Rats

    PubMed Central

    Liu, Min; Gao, Rui; Meng, Qingwei; Zhang, Yuanyuan; Bi, Chongpeng; Shan, Anshan

    2014-01-01

    The present study was conducted to investigate the effects of maternal zearalenone (ZEN) exposure on the intestine of pregnant Sprague-Dawley (SD) rats and its offspring. Ninety-six pregnant SD rats were randomly divided into four groups and were fed with diets containing ZEN at concentrations of 0.3 mg/kg, 48.5 mg/kg, 97.6 mg/kg or 146.0 mg/kg from gestation days (GD) 1 to 7. All rats were fed with mycotoxin-free diet until their offspring were weaned at three weeks of age. The small intestinal fragments from pregnant rats at GD8, weaned dams and pups were collected and studied for toxic effects of ZEN on antioxidant status, immune response, expression of junction proteins, and morphology. The results showed that ZEN induced oxidative stress, affected the villous structure and reduced the expression of junction proteins claudin-4, occludin and connexin43 (Cx43) in a dose-dependent manner in pregnant rats. Different effects on the expression of cytokines were also observed both in mRNA and protein levels in these pregnant groups. Ingestion of high levels of ZEN caused irreversible damage in weaned dams, such as oxidative stress, decreased villi hight and low expression of junction proteins and cytokines. Decreased expression of jejunal interleukin-8 (IL-8) and increased expression of gastrointestinal glutathione peroxidase (GPx2) mRNA were detected in weaned offspring, indicating long-term damage caused by maternal ZEN. We also found that the Nrf2 expression both in mRNA and protein levels were up-regulated in the ZEN-treated groups of pregnant dams and the high-dose of ZEN group of weaned dams. The data indicate that modulation of Nrf2-mediated pathway is one of mechanism via which ZEN affects gut wall antioxidant and inflammatory responses. PMID:25180673

  17. Toxic effects of maternal zearalenone exposure on intestinal oxidative stress, barrier function, immunological and morphological changes in rats.

    PubMed

    Liu, Min; Gao, Rui; Meng, Qingwei; Zhang, Yuanyuan; Bi, Chongpeng; Shan, Anshan

    2014-01-01

    The present study was conducted to investigate the effects of maternal zearalenone (ZEN) exposure on the intestine of pregnant Sprague-Dawley (SD) rats and its offspring. Ninety-six pregnant SD rats were randomly divided into four groups and were fed with diets containing ZEN at concentrations of 0.3 mg/kg, 48.5 mg/kg, 97.6 mg/kg or 146.0 mg/kg from gestation days (GD) 1 to 7. All rats were fed with mycotoxin-free diet until their offspring were weaned at three weeks of age. The small intestinal fragments from pregnant rats at GD8, weaned dams and pups were collected and studied for toxic effects of ZEN on antioxidant status, immune response, expression of junction proteins, and morphology. The results showed that ZEN induced oxidative stress, affected the villous structure and reduced the expression of junction proteins claudin-4, occludin and connexin43 (Cx43) in a dose-dependent manner in pregnant rats. Different effects on the expression of cytokines were also observed both in mRNA and protein levels in these pregnant groups. Ingestion of high levels of ZEN caused irreversible damage in weaned dams, such as oxidative stress, decreased villi hight and low expression of junction proteins and cytokines. Decreased expression of jejunal interleukin-8 (IL-8) and increased expression of gastrointestinal glutathione peroxidase (GPx2) mRNA were detected in weaned offspring, indicating long-term damage caused by maternal ZEN. We also found that the Nrf2 expression both in mRNA and protein levels were up-regulated in the ZEN-treated groups of pregnant dams and the high-dose of ZEN group of weaned dams. The data indicate that modulation of Nrf2-mediated pathway is one of mechanism via which ZEN affects gut wall antioxidant and inflammatory responses.

  18. Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

    PubMed

    Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

    2015-11-04

    Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets.

  19. Size- and support-dependent evolution of the oxidation state and structure by oxidation of subnanometer cobalt clusters.

    PubMed

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7, and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) and near-edge X-ray absorption fine structure (NEXAFS) were used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co(2+) phase was identified in all samples. However, XANES analysis of cobalt clusters on UNCD showed that ∼10% fraction of a Co(0) phase was identified for all three cluster sizes and about 30 and 12% fraction of a Co(3+) phase in 4, 7, and 27 atom clusters, respectively. In the alumina-supported clusters, the dominating Co(2+) component was attributed to a cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure to a great extent follows the tetrahedral morphology of the support. All supported clusters were found to be resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  20. Keap1 redox-dependent regulation of doxorubicin-induced oxidative stress response in cardiac myoblasts

    SciTech Connect

    Nordgren, Kendra K.S. Wallace, Kendall B.

    2014-01-01

    Doxorubicin (DOX) is a widely prescribed treatment for a broad scope of cancers, but clinical utility is limited by the cumulative, dose-dependent cardiomyopathy that occurs with repeated administration. DOX-induced cardiotoxicity is associated with the production of reactive oxygen species (ROS) and oxidation of lipids, DNA and proteins. A major cellular defense mechanism against such oxidative stress is activation of the Keap1/Nrf2-antioxidant response element (ARE) signaling pathway, which transcriptionally regulates expression of antioxidant genes such as Nqo1 and Gstp1. In the present study, we address the hypothesis that an initial event associated with DOX-induced oxidative stress is activation of the Keap1/Nrf2-dependent expression of antioxidant genes and that this is regulated through drug-induced changes in redox status of the Keap1 protein. Incubation of H9c2 rat cardiac myoblasts with DOX resulted in a time- and dose-dependent decrease in non-protein sulfhydryl groups. Associated with this was a near 2-fold increase in Nrf2 protein content and enhanced transcription of several of the Nrf2-regulated down-stream genes, including Gstp1, Ugt1a1, and Nqo1; the expression of Nfe2l2 (Nrf2) itself was unaltered. Furthermore, both the redox status and the total amount of Keap1 protein were significantly decreased by DOX, with the loss of Keap1 being due to both inhibited gene expression and increased autophagic, but not proteasomal, degradation. These findings identify the Keap1/Nrf2 pathway as a potentially important initial response to acute DOX-induced oxidative injury, with the primary regulatory events being the oxidation and autophagic degradation of the redox sensor Keap1 protein. - Highlights: • DOX caused a ∼2-fold increase in Nrf2 protein content. • DOX enhanced transcription of several Nrf2-regulated down-stream genes. • Redox status and total amount of Keap1 protein were significantly decreased by DOX. • Loss of Keap1 protein was due to

  1. Effect of Oxidation Rate and Fe(II) State on Microbial Nitrate-Dependent Fe(III) Mineral Formation

    PubMed Central

    Senko, John M.; Dewers, Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems. PMID:16269756

  2. Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

    USGS Publications Warehouse

    Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  3. Overexpression of actin-depolymerizing factor blocks oxidized low-density lipoprotein-induced mouse brain microvascular endothelial cell barrier dysfunction.

    PubMed

    Wang, Jun; Sun, Lu; Si, Yan-Fang; Li, Bao-Min

    2012-12-01

    The aim of present work was to elucidate the role of actin-depolymerizing factor (ADF), an important regulator of actin cytoskeleton, in the oxidized low-density lipoprotein (ox-LDL)-induced blood-brain barrier (BBB) disruption. The primary mouse brain microvascular endothelial cells (MBMECs) were exposed to ox-LDL. Treatment with LDL served as control. It was found that ADF mRNA level and protein expression were decreased when exposed to ox-LDL in MBMECs. Then, we investigated the influence of ADF overexpression on ox-LDL-treated MBMECs. Structurally, overexpression of ADF inhibited ox-LDL-induced F-actin formation. Functionally, overexpression of ADF attenuated ox-LDL-induced disruption of endothelial barrier marked by restoration of transendothelial electrical resistance, permeability of Evans Blue and expression of tight junction-associated proteins including ZO-1 and occludin, and blocked ox-LDL-induced oxidative stress marked by inhibition of reactive oxygen species (ROS) formation and activity of NADPH oxidase and Nox2 expression. However, overexpression of ADF in control cells had no significant effect on endothelial permeability and ROS formation. In conclusion, overexpression of ADF blocks ox-LDL-induced disruption of endothelial barrier. In addition, siRNA-mediated downregulation of ADF expression aggravated ox-LDL-induced disruption of endothelial barrier and ROS formation. These findings identify ADF as a key signaling molecule in the regulation of BBB integrity and suggest that ADF might be used as a target to modulate diseases accompanied by ox-LDL-induced BBB compromise.

  4. Improved tolerance of acute severe hypoxic stress in chronic hypoxic diaphragm is nitric oxide-dependent.

    PubMed

    Lewis, Philip; McMorrow, Clodagh; Bradford, Aidan; O'Halloran, Ken D

    2015-09-01

    The effects of chronic hypoxia (CH) on respiratory muscle performance have hardly been investigated, despite clinical relevance. Results from recent studies are indicative of unique adaptive strategies in hypoxic diaphragm. Respiratory muscle tolerance of acute severe hypoxic stress was examined in normoxic and CH diaphragm in the presence and absence of a nitric oxide (NO) synthase inhibitor. We tested the hypothesis that improved tolerance of severe hypoxic stress in CH diaphragm is NO-dependent. Wistar rats were exposed to normoxia (sea-level, n = 6) or CH (ambient pressure = 380 mmHg, n = 6) for 6 weeks. Diaphragm muscle functional properties were determined ex vivo under severe hypoxic conditions (gassed with 95%N2/5% CO2) with and without 1 mM L-N(G)-nitroarginine (L-NNA, nNOS inhibitor). Fatigue tolerance, but not force, was significantly improved in CH diaphragm (p = 0.008). CH exposure did not affect diaphragm muscle fibre oxidative capacity determined from cluster analysis of area-density plots of muscle fibre succinate dehydrogenase activity. Acute NOS inhibition reduced diaphragm peak tetanic force (p = 0.018), irrespective of gas treatment, and completely reversed improved fatigue tolerance of the CH diaphragm. We conclude that CH exposure improves fatigue tolerance during acute severe hypoxic stress in an NO-dependent manner, independent of muscle fibre oxidative capacity.

  5. Infertility and recurrent miscarriage with complex II deficiency-dependent mitochondrial oxidative stress in animal models.

    PubMed

    Ishii, Takamasa; Yasuda, Kayo; Miyazawa, Masaki; Mitsushita, Junji; Johnson, Thomas E; Hartman, Phil S; Ishii, Naoaki

    2016-04-01

    Oxidative stress is associated with some forms of both male and female infertility. However, there is insufficient knowledge of the influence of oxidative stress on the maintenance of a viable pregnancy, including pregnancy complications and fetal development. There are a number of animal models for understanding age-dependent decrease of reproductive ability and diabetic embryopathy, especially abnormal spermatogenesis, oogenesis and embryogenesis with mitochondrial dysfunctions. Several important processes occur in mitochondria, including ATP synthesis, calcium ion storage, induction of apoptosis and production of reactive oxygen species (ROS). These events have different effects on the several aspects of reproductive function. Tet-mev-1 conditional transgenic mice, developed after studies with the mev-1 mutant of the nematode C. elegans, offer the ability to carefully regulate expression of doxycycline-induced mutated SDHC(V69E) levels and hence modulate endogenous oxidative stress. The mev-1 models have served to illuminate the effects of complex II deficiency-dependent mitochondrial ROS production, although interestingly they maintain normal mitochondrial and intracellular ATP levels. In this review, the reproductive dysfunctions are presented focusing on fertility potentials in each gamete, early embryogenesis, maternal conditions with placental function and neonatal development.

  6. Energy-dependent relaxation time in quaternary amorphous oxide semiconductors probed by gated Hall effect measurements

    NASA Astrophysics Data System (ADS)

    Socratous, Josephine; Watanabe, Shun; Banger, Kulbinder K.; Warwick, Christopher N.; Branquinho, Rita; Barquinha, Pedro; Martins, Rodrigo; Fortunato, Elvira; Sirringhaus, Henning

    2017-01-01

    Despite the success of exploiting the properties of amorphous oxide semiconductors for device applications, the charge transport in these materials is still not clearly understood. The observation of a definite Hall voltage suggests that electron transport in the conduction band is free-electron-like. However, the temperature dependence of the Hall and field-effect mobilities cannot be explained using a simple bandlike model. Here, we perform gated Hall effect measurements in field-effect transistors, which allow us to make two independent estimates of the charge carrier concentration and determine the Hall factor providing information on the energy dependence of the relaxation time. We demonstrate that the Hall factor in a range of sputtered and solution-processed quaternary amorphous oxides, such as a-InGaZnO, is close to two, while in ternary oxides, such as InZnO, it is near unity. This suggests that quaternary elements like Ga act as strong ionized impurity scattering centers in these materials.

  7. Microbial nitrate-dependent cyclohexane degradation coupled with anaerobic ammonium oxidation.

    PubMed

    Musat, Florin; Wilkes, Heinz; Behrends, Astrid; Woebken, Dagmar; Widdel, Friedrich

    2010-10-01

    An anaerobic nitrate-reducing enrichment culture was established with a cyclic saturated petroleum hydrocarbon, cyclohexane, the fate of which in anoxic environments has been scarcely investigated. GC-MS showed cyclohexylsuccinate as a metabolite, in accordance with an anaerobic enzymatic activation of cyclohexane by carbon-carbon addition to fumarate. Furthermore, long-chain cyclohexyl-substituted cell fatty acids apparently derived from cyclohexane were detected. Nitrate reduction was not only associated with cyclohexane utilization but also with striking depletion of added ammonium ions. Significantly more ammonium was consumed than could be accounted for by assimilation. This indicated the occurrence of anaerobic ammonium oxidation (anammox) with nitrite from cyclohexane-dependent nitrate reduction. Indeed, nitrite depletion was stimulated upon further addition of ammonium. Analysis of 16S rRNA genes and subsequent cell hybridization with specific probes showed that approximately 75% of the bacterial cells affiliated with the Geobacteraceae and approximately 18% with Candidatus 'Brocadia anammoxidans' (member of the Planctomycetales), an anaerobic ammonium oxidizer. These results and additional quantitative growth experiments indicated that the member of the Geobacteraceae reduced nitrate with cyclohexane to nitrite and some ammonium; the latter two and ammonium added to the medium were scavenged by anammox bacteria to yield dinitrogen. A model was established to quantify the partition of each microorganism in the overall process. Such hydrocarbon oxidation by an alleged 'denitrification' ('pseudo-denitrification'), which in reality is a dissimilatory loop through anammox, can in principle also occur in other microbial systems with nitrate-dependent hydrocarbon attenuation.

  8. Endoplasmic Reticulum Oxidative Stress Triggers Tgf-Beta-Dependent Muscle Dysfunction by Accelerating Ascorbic Acid Turnover

    PubMed Central

    Pozzer, Diego; Favellato, Mariagrazia; Bolis, Marco; Invernizzi, Roberto William; Solagna, Francesca; Blaauw, Bert; Zito, Ester

    2017-01-01

    Endoplasmic reticulum (ER) and oxidative stress are two related phenomena that have important metabolic consequences. As many skeletal muscle diseases are triggered by oxidative stress, we explored the chain of events linking a hyperoxidized ER (which causes ER and oxidative stress) with skeletal muscle dysfunction. An unbiased exon expression array showed that the combined genetic modulation of the two master ER redox proteins, selenoprotein N (SEPN1) and endoplasmic oxidoreductin 1 (ERO1), led to an SEPN1-related myopathic phenotype due to excessive signalling of transforming growth factor (TGF)-beta. The increased TGF-beta activity in the genetic mutants was caused by accelerated turnover of the ER localized (anti-oxidant) ascorbic acid that affected collagen deposition in the extracellular matrix. In a mouse mutant of SEPN1, which is dependent on exogenous ascorbic acid, a limited intake of ascorbic acid revealed a myopathic phenotype as a consequence of an altered TGF-beta signalling. Indeed, systemic antagonism of TGF-beta re-established skeletal muscle function in SEPN1 mutant mice. In conclusion, this study sheds new light on the molecular mechanism of SEPN1-related myopathies and indicates that the TGF-beta/ERO1/ascorbic acid axis offers potential for their treatment. PMID:28106121

  9. Kaempferol derivatives prevent oxidative stress-induced cell death in a DJ-1-dependent manner.

    PubMed

    Qu, Wei; Fan, Li; Kim, Yun-chul; Ishikawa, Shizuma; Iguchi-Ariga, Sanae M M; Pu, Xiao-Ping; Ariga, Hiroyoshi

    2009-06-01

    DJ-1, a causative gene product of a familial form of Parkinson's disease (PD), PARK7, plays a role in anti-oxidative stress, and loss of its function is thought to result in the onset of PD. Superfluous oxidation of cysteine at amino acid 106 (C106) of DJ-1 renders DJ-1 inactive, and such oxidized DJ-1 was observed in patients with the sporadic form of PD. In this study, we examined the relationship between DJ-1 and compounds extracted from traditional Chinese medicines possessing anti-oxidant activity. Of the 12 compounds tested, 5 were found to specifically bind to the C106 region by using a quartz crystal microbalance. Although 4 compounds prevented rat PC12 and primary neuronal cells from undergoing H2O2-induced cell death, the protective activity of 2 compounds, kaempferol 3-O-beta-rutinoside and 6-hydroxykaempferol 3,6-di-O-beta-D-glucoside, was diminished in cells transfected with siRNA targeting DJ-1, indicating DJ-1-dependent reaction of these compounds. Furthermore, these compounds reduced the level of reactive oxygen species and restored tyrosine hydroxylase activity that had been induced and compromised, respectively, by treatment of cells with H2O2. The results suggest that these compounds are useful lead compounds for PD therapy.

  10. Oxidative stress–dependent phosphorylation activates ZNRF1 to induce neuronal/axonal degeneration

    PubMed Central

    Wakatsuki, Shuji; Furuno, Akiko; Ohshima, Makiko

    2015-01-01

    Oxidative stress is a well-known inducer of neuronal apoptosis and axonal degeneration. We previously showed that the E3 ubiquitin ligase ZNRF1 promotes Wallerian degeneration by degrading AKT to induce GSK3B activation. We now demonstrate that oxidative stress serves as an activator of the ubiquitin ligase activity of ZNRF1 by inducing epidermal growth factor receptor (EGFR)–mediated phosphorylation at the 103rd tyrosine residue and that the up-regulation of ZNRF1 activity by oxidative stress leads to neuronal apoptosis and Wallerian degeneration. We also show that nicotinamide adenine dinucleotide phosphate–reduced oxidase activity is required for the EGFR-dependent phosphorylation-induced activation of ZNRF1 and resultant AKT degradation via the ubiquitin proteasome system to induce Wallerian degeneration. These results indicate the pathophysiological significance of the EGFR–ZNRF1 pathway induced by oxidative stress in the regulation of neuronal apoptosis and Wallerian degeneration. A deeper understanding of the regulatory mechanism for ZNRF1 catalytic activity via phosphorylation will provide a potential therapeutic avenue for neurodegeneration. PMID:26572622

  11. Oxidation-induced calcium-dependent dehydration of normal human red blood cells.

    PubMed

    Shcherbachenko, Irina M; Lisovskaya, Irina L; Tikhonov, Vladimir P

    2007-05-01

    Phenazine-methosulphate (PMS) is a strong oxidant that induces reactive oxygen species (ROS) formation in cells. Though it has been shown that PMS increases the red blood cell (RBC) membrane permeability to K(+), the hypotheses on the mechanism of PMS-induced effects are contradictory and there are no data on volume changes induced by this oxidant. Therefore, the influence of the PMS + ascorbate oxidative system on the volume of normal human RBCs was studied. In a Ca(2 + )-containing medium, PMS + ascorbate caused dehydration (shrinking) of RBCs judged by: (1) changes in the density and osmotic resistance distributions of RBCs, and (2) a decrease in their low-angle scattering assessed by FACS analysis. The dehydration resulted from activation of the Gardos channels, was PMS and ascorbate concentration-dependent, was associated with broadening of the density and osmotic resistance distributions of the RBCs, and decreased in the presence of the taxifolin and rutin antioxidants. These findings contribute to a better understanding of the physiology and pathology of oxidatively-modified RBCs and may be of practical significance in estimating the antioxidant activity of various substances.

  12. Streptomyces natalensis programmed cell death and morphological differentiation are dependent on oxidative stress

    PubMed Central

    Beites, Tiago; Oliveira, Paulo; Rioseras, Beatriz; Pires, Sílvia D. S.; Oliveira, Rute; Tamagnini, Paula; Moradas-Ferreira, Pedro; Manteca, Ángel; Mendes, Marta V.

    2015-01-01

    Streptomyces are aerobic Gram-positive bacteria characterized by a complex life cycle that includes hyphae differentiation and spore formation. Morphological differentiation is triggered by stressful conditions and takes place in a pro-oxidant environment, which sets the basis for an involvement of the oxidative stress response in this cellular process. Characterization of the phenotypic traits of Streptomyces natalensis ΔkatA1 (mono-functional catalase) and ΔcatR (Fur-like repressor of katA1 expression) strains in solid medium revealed that both mutants had an impaired morphological development process. The sub-lethal oxidative stress caused by the absence of KatA1 resulted in the formation of a highly proliferative and undifferentiated vegetative mycelium, whereas de-repression of CatR regulon, from which KatA1 is the only known representative, resulted in the formation of scarce aerial mycelium. Both mutant strains had the transcription of genes associated with aerial mycelium formation and biosynthesis of the hyphae hydrophobic layer down-regulated. The first round of the programmed cell death (PCD) was inhibited in both strains which caused the prevalence of the transient primary mycelium (MI) over secondary mycelium (MII). Our data shows that the first round of PCD and morphological differentiation in S. natalensis is dependent on oxidative stress in the right amount at the right time. PMID:26256439

  13. Theoretical approach to description of time-dependent nitric oxide effects in the vasculature.

    PubMed

    Seraya, I P; Nartsissov, Ya R

    2002-01-01

    Nitric oxide (NO) is one of the most important signal compounds in a living cell. As a typical free radical it has both toxic and physiological effects and their balance is determined by a spatial distribution of NO concentration. Moreover, some biological functions, especially NO-mediated relaxation of blood vessels, have to be time-limited. In order to circumscribe this phenomenon non steady-state mathematical model has been used for description of nitric oxide diffusion in vascular smooth muscle. It was shown that the microvascular relaxation could be observed even after a short time of NO production in the endothelium. This time is up to 3 times below that needed to reach the steady-state spatial NO gradient. However, the effect of nitric oxide essentially depends on the rate of NO production and blood vessel diameter. Furthermore, non steady-state nitric oxide concentration gradient was represented as an analytical function of time and coordinate. It is essential that this function describes a common case of one-dimensional diffusion of uncharged low-mass molecules. Thus, the results can be used for calculation of an upper estimation of experimental data.

  14. Atomic layer deposited lithium aluminum oxide: (In)dependency of film properties from pulsing sequence

    SciTech Connect

    Miikkulainen, Ville Nilsen, Ola; Fjellvåg, Helmer; Li, Han; King, Sean W.; Laitinen, Mikko; Sajavaara, Timo

    2015-01-01

    Atomic layer deposition (ALD) holds markedly high potential of becoming the enabling method for achieving the three-dimensional all-solid-state thin-film lithium ion battery (LiB). One of the most crucial components in such a battery is the electrolyte that needs to hold both low electronic conductivity and at least fair lithium ion conductivity being at the same time pinhole free. To obtain these desired properties in an electrolyte film, one necessarily has to have a good control over the elemental composition of the deposited material. The present study reports on the properties of ALD lithium aluminum oxide (Li{sub x}Al{sub y}O{sub z}) thin films. In addition to LiB electrolyte applications, Li{sub x}Al{sub y}O{sub z} is also a candidate low dielectric constant (low-k) etch stop and diffusion barrier material in nanoelectronics applications. The Li{sub x}Al{sub y}O{sub z} films were deposited employing trimethylaluminum-O{sub 3} and lithium tert-butoxide-H{sub 2}O for Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, respectively. The composition was aimed to be controlled by varying the pulsing ratio of those two binary oxide ALD cycles. The films were characterized by several methods for composition, crystallinity and phase, electrical properties, hardness, porosity, and chemical environment. Regardless of the applied pulsing ratio of Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, all the studied ALD Li{sub x}Al{sub y}O{sub z} films of 200 and 400 nm in thickness were polycrystalline in the orthorhombic β-LiAlO{sub 2} phase and also very similar to each other with respect to composition and other studied properties. The results are discussed in the context of both fundamental ALD chemistry and applicability of the films as thin-film LiB electrolytes and low-k etch stop and diffusion barriers.

  15. Article Including Environmental Barrier Coating System

    NASA Technical Reports Server (NTRS)

    Lee, Kang N. (Inventor)

    2015-01-01

    An enhanced environmental barrier coating for a silicon containing substrate. The enhanced barrier coating may include a bond coat doped with at least one of an alkali metal oxide and an alkali earth metal oxide. The enhanced barrier coating may include a composite mullite bond coat including BSAS and another distinct second phase oxide applied over said surface.

  16. ADAM17/EGFR axis promotes transglutaminase-dependent skin barrier formation through phosholipase C γ1 and protein kinase C pathways

    PubMed Central

    Wolf , Cristina; Qian, Yawen; Brooke, Matthew A.; Kelsell, David P.; Franzke, Claus-Werner

    2016-01-01

    The vitally important skin barrier is formed by extensive cross-linking activity of transglutaminases (TGs) during terminal epidermal differentiation. We have previously shown that epidermal deficiency of a disintegrin and metalloproteinase 17 (ADAM17), the principal EGFR ligand sheddase, results in postnatal skin barrier defects in mice due to impeded TG activity. However, the mechanism by which ADAM17/EGFR signalling maintains TG activity during epidermal differentiation remains elusive. Here we demonstrate that ADAM17-dependent EGFR signalling promotes TG activity in keratinocytes committed to terminal differentiation by direct induction of TG1 expression. Restored TG1 expression of EGF-stimulated differentiated Adam17−/− keratinocytes was strongly repressed by inhibitors for PLCγ1 or protein kinase C (PKC) pathways, while treatment with the PKC stimulator 12-O-tetradecanoylphorbol-13-acetate restored TG activity in the epidermis of keratinocyte-specific Adam17−/− (AD17ΔKC) mice. Further investigations emphasized the expression of PKCη, a mediator of TGM1 transcription, to be sensitive to EGFR activation. In agreement, topical skin application of cholesterol sulfate, an activator of PKCη, significantly improved TG activity in epidermis of AD17ΔKC mice. Our results suggest ADAM17/EGFR-driven PLCγ1 and PKC pathways as important promoters of TG1 expression during terminal keratinocyte differentiation. These findings may help to identify new therapeutic targets for inflammatory skin diseases related to epidermal barrier defects. PMID:28004780

  17. Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts.

    PubMed

    Cao, Shaowen; Tao, Franklin Feng; Tang, Yu; Li, Yuting; Yu, Jiaguo

    2016-08-22

    Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.

  18. Salmon-derived thrombin inhibits development of chronic pain through an endothelial barrier protective mechanism dependent on APC

    PubMed Central

    Smith, Jenell R; Galie, Peter A; Slochower, David R; Weisshaar, Christine L.; Janmey, Paul A; Winkelstein, Beth A

    2015-01-01

    Many neurological disorders are initiated by blood-brain barrier breakdown, which potentiates spinal neuroinflammation and neurodegeneration. Peripheral neuropathic injuries are known to disrupt the blood-spinal cord barrier (BSCB) and to potentiate inflammation. But, it is not known whether BSCB breakdown facilitates pain development. In this study, a neural compression model in the rat was used to evaluate relationships among BSCB permeability, inflammation and pain-related behaviors. BSCB permeability increases transiently only after injury that induces mechanical hyperalgesia, which correlates with serum concentrations of pro-inflammatory cytokines, IL-7, IL-12, IL-1α and TNF-α. Mammalian thrombin dually regulates vascular permeability through PAR1 and activated protein C (APC). Since thrombin protects vascular integrity through APC, directing its affinity towards protein C, while still promoting coagulation, might be an ideal treatment for BSCB-disrupting disorders. Salmon thrombin, which prevents the development of mechanical allodynia, also prevents BSCB breakdown after neural injury and actively inhibits TNF-α-induced endothelial permeability in vitro, which is not evident the case for human thrombin. Salmon thrombin’s production of APC faster than human thrombin is confirmed using a fluorogenic assay and APC is shown to inhibit BSCB breakdown and pain-related behaviors similar to salmon thrombin. Together, these studies highlight the impact of BSCB on pain and establish salmon thrombin as an effective blocker of BSCB, and resulting nociception, through its preferential affinity for protein C. PMID:26708087

  19. Dependence of the critical temperature in overdoped copper oxides on superfluid density.

    PubMed

    Božović, I; He, X; Wu, J; Bollinger, A T

    2016-08-18

    The physics of underdoped copper oxide superconductors, including the pseudogap, spin and charge ordering and their relation to superconductivity, is intensely debated. The overdoped copper oxides are perceived as simpler, with strongly correlated fermion physics evolving smoothly into the conventional Bardeen-Cooper-Schrieffer behaviour. Pioneering studies on a few overdoped samples indicated that the superfluid density was much lower than expected, but this was attributed to pair-breaking, disorder and phase separation. Here we report the way in which the magnetic penetration depth and the phase stiffness depend on temperature and doping by investigating the entire overdoped side of the La2-xSrxCuO4 phase diagram. We measured the absolute values of the magnetic penetration depth and the phase stiffness to an accuracy of one per cent in thousands of samples; the large statistics reveal clear trends and intrinsic properties. The films are homogeneous; variations in the critical superconducting temperature within a film are very small (less than one kelvin). At every level of doping the phase stiffness decreases linearly with temperature. The dependence of the zero-temperature phase stiffness on the critical superconducting temperature is generally linear, but with an offset; however, close to the origin this dependence becomes parabolic. This scaling law is incompatible with the standard Bardeen-Cooper-Schrieffer description.

  20. Calcium co-regulates oxidative metabolism and ATP synthase-dependent respiration in pancreatic beta cells.

    PubMed

    De Marchi, Umberto; Thevenet, Jonathan; Hermant, Aurelie; Dioum, Elhadji; Wiederkehr, Andreas

    2014-03-28

    Mitochondrial energy metabolism is essential for glucose-induced calcium signaling and, therefore, insulin granule exocytosis in pancreatic beta cells. Calcium signals are sensed by mitochondria acting in concert with mitochondrial substrates for the full activation of the organelle. Here we have studied glucose-induced calcium signaling and energy metabolism in INS-1E insulinoma cells and human islet beta cells. In insulin secreting cells a surprisingly large fraction of total respiration under resting conditions is ATP synthase-independent. We observe that ATP synthase-dependent respiration is markedly increased after glucose stimulation. Glucose also causes a very rapid elevation of oxidative metabolism as was followed by NAD(P)H autofluorescence. However, neither the rate of the glucose-induced increase nor the new steady-state NAD(P)H levels are significantly affected by calcium. Our findings challenge the current view, which has focused mainly on calcium-sensitive dehydrogenases as the target for the activation of mitochondrial energy metabolism. We propose a model of tight calcium-dependent regulation of oxidative metabolism and ATP synthase-dependent respiration in beta cell mitochondria. Coordinated activation of matrix dehydrogenases and respiratory chain activity by calcium allows the respiratory rate to change severalfold with only small or no alterations of the NAD(P)H/NAD(P)(+) ratio.

  1. Copper-dependent inhibition and oxidative inactivation with affinity cleavage of yeast glutathione reductase.

    PubMed

    Murakami, Keiko; Tsubouchi, Ryoko; Fukayama, Minoru; Yoshino, Masataka

    2014-06-01

    Effects of copper on the activity and oxidative inactivation of yeast glutathione reductase were analyzed. Glutathione reductase from yeast was inhibited by cupric ion and more potently by cuprous ion. Copper ion inhibited the enzyme noncompetitively with respect to the substrate GSSG and NADPH. The Ki values of the enzyme for Cu(2+) and Cu(+) ion were determined to be 1 and 0.35 μM, respectively. Copper-dependent inactivation of glutathione reductase was also analyzed. Hydrogen peroxide and copper/ascorbate also caused an inactivation with the cleavage of peptide bond of the enzyme. The inactivation/fragmentation of the enzyme was prevented by addition of catalase, suggesting that hydroxyl radical produced through the cuprous ion-dependent reduction of oxygen is responsible for the inactivation/fragmentation of the enzyme. SDS-PAGE and TOF-MS analysis confirmed eight fragments, which were further determined to result from the cleavage of the Met17-Ser18, Asn20-Thr21, Glu251-Gly252, Ser420-Pro421, Pro421-Thr422 bonds of the enzyme by amino-terminal sequencing analysis. Based on the kinetic analysis and no protective effect of the substrates, GSSG and NADPH on the copper-mediated inactivation/fragmentation of the enzyme, copper binds to the sites apart from the substrate-sites, causing the peptide cleavage by hydroxyl radical. Copper-dependent oxidative inactivation/fragmentation of glutathione reductase can explain the prooxidant properties of copper under the in vivo conditions.

  2. Dependence of the critical temperature in overdoped copper oxides on superfluid density

    NASA Astrophysics Data System (ADS)

    Božović, I.; He, X.; Wu, J.; Bollinger, A. T.

    2016-08-01

    The physics of underdoped copper oxide superconductors, including the pseudogap, spin and charge ordering and their relation to superconductivity, is intensely debated. The overdoped copper oxides are perceived as simpler, with strongly correlated fermion physics evolving smoothly into the conventional Bardeen-Cooper-Schrieffer behaviour. Pioneering studies on a few overdoped samples indicated that the superfluid density was much lower than expected, but this was attributed to pair-breaking, disorder and phase separation. Here we report the way in which the magnetic penetration depth and the phase stiffness depend on temperature and doping by investigating the entire overdoped side of the La2-xSrxCuO4 phase diagram. We measured the absolute values of the magnetic penetration depth and the phase stiffness to an accuracy of one per cent in thousands of samples; the large statistics reveal clear trends and intrinsic properties. The films are homogeneous; variations in the critical superconducting temperature within a film are very small (less than one kelvin). At every level of doping the phase stiffness decreases linearly with temperature. The dependence of the zero-temperature phase stiffness on the critical superconducting temperature is generally linear, but with an offset; however, close to the origin this dependence becomes parabolic. This scaling law is incompatible with the standard Bardeen-Cooper-Schrieffer description.

  3. Tailoring morphology in free-standing anodic aluminium oxide: control of barrier layer opening down to the sub-10 nm diameter.

    PubMed

    Gong, Jie; Butler, William H; Zangari, Giovanni

    2010-05-01

    Free-standing, highly ordered porous aluminium oxide templates were fabricated by three-step anodization in oxalic, sulfuric or phosphoric acid solutions, followed by dissolution of the aluminium substrate in HgCl(2). Opening of the pore bottoms on the barrier layer side of these templates was carried out by using chemical or ion beam etching. Chemical etching is capable of achieving full pore opening, but partial pore opening occurs inhomogeneously. On the contrary, ion beam etching enables homogeneous and reproducible partial pore opening, with the pore size controlled through the etching time. By this method, pore openings as small as 5 nm can reliably be obtained.

  4. eNOS-derived nitric oxide regulates endothelial barrier function through VE-cadherin and Rho GTPases

    PubMed Central

    Di Lorenzo, Annarita; Lin, Michelle I.; Murata, Takahisa; Landskroner-Eiger, Shira; Schleicher, Michael; Kothiya, Milankumar; Iwakiri, Yasuko; Yu, Jun; Huang, Paul L.; Sessa, William C.

    2013-01-01

    Summary Transient disruption of endothelial adherens junctions and cytoskeletal remodeling are responsible for increases in vascular permeability induced by inflammatory stimuli and vascular endothelial growth factor (VEGF). Nitric oxide (NO) produced by endothelial NO synthase (eNOS) is crucial for VEGF-induced changes in permeability in vivo; however, the molecular mechanism by which endogenous NO modulates endothelial permeability is not clear. Here, we show that the lack of eNOS reduces VEGF-induced permeability, an effect mediated by enhanced activation of the Rac GTPase and stabilization of cortical actin. The loss of NO increased the recruitment of the Rac guanine-nucleotide-exchange factor (GEF) TIAM1 to adherens junctions and VE-cadherin (also known as cadherin 5), and reduced Rho activation and stress fiber formation. In addition, NO deficiency reduced VEGF-induced VE-cadherin phosphorylation and impaired the localization, but not the activation, of c-Src to cell junctions. The physiological role of eNOS activation is clear given that VEGF-, histamine- and inflammation-induced vascular permeability is reduced in mice bearing a non-phosphorylatable knock-in mutation of the key eNOS phosphorylation site S1176. Thus, NO is crucial for Rho GTPase-dependent regulation of cytoskeletal architecture leading to reversible changes in vascular permeability. PMID:24046447

  5. Epirubicin-loaded superparamagnetic iron-oxide nanoparticles for transdermal delivery: cancer therapy by circumventing the skin barrier.

    PubMed

    Rao, Yue-feng; Chen, Wei; Liang, Xing-guang; Huang, Yong-zhuo; Miao, Jing; Liu, Lin; Lou, Yan; Zhang, Xing-guo; Wang, Ben; Tang, Rui-kang; Chen, Zhong; Lu, Xiao-yang

    2015-01-14

    The transdermal administration of chemotherapeutic agents is a persistent challenge for tumor treatments. A model anticancer agent, epirubicin (EPI), is attached to functionalized superparamagnetic iron-oxide nanoparticles (SPION). The covalent modification of the SPION results in EPI-SPION, a potential drug delivery vector that uses magnetism for the targeted transdermal chemotherapy of skin tumors. The spherical EPI-SPION composite exhibits excellent magnetic responsiveness with a saturation magnetization intensity of 77.8 emu g(-1) . They feature specific pH-sensitive drug release, targeting the acidic microenvironment typical in common tumor tissues or endosomes/lysosomes. Cellular uptake studies using human keratinocyte HaCaT cells and melanoma WM266 cells demonstrate that SPION have good biocompatibility. After conjugation with EPI, the nanoparticles can inhibit WM266 cell proliferation; its inhibitory effect on tumor proliferation is determined to be dose-dependent. In vitro transdermal studies demonstrate that the EPI-SPION composites can penetrate deep inside the skin driven by an external magnetic field. The magnetic-field-assisted SPION transdermal vector can circumvent the stratum corneum via follicular pathways. The study indicates the potential of a SPION-based vector for feasible transdermal therapy of skin cancer.

  6. Dopamine-melanin film deposition depends on the used oxidant and buffer solution.

    PubMed

    Bernsmann, Falk; Ball, Vincent; Addiego, Frédéric; Ponche, Arnaud; Michel, Marc; Gracio, José Joaquin de Almeida; Toniazzo, Valérie; Ruch, David

    2011-03-15

    The deposition of "polydopamine" films, from an aqueous solution containing dopamine or other catecholamines, constitutes a new and versatile way to functionalize solid-liquid interfaces. Indeed such films can be deposited on almost all kinds of materials. Their deposition kinetics does not depend markedly on the surface chemistry of the substrate, and the films can reach thickness of a few tens of nanometers in a single reaction step. Up to now, even if a lot is known about the oxidation mechanism of dopamine in solution, only little information is available to describe the deposition mechanism on surfaces either by oxidation in solution or by electrodeposition. The deposition kinetics of melanin was only investigated from dopamine solutions using oxygen or ammonium persulfate as an oxidant and from a tris(hydroxymethyl) aminomethane (Tris) containing buffer solutions at pH 8.5. Many other oxidants could be used, and the buffer agent containing a primary amine group may influence the deposition process. Herein we show that the deposition kinetics of melanin from dopamine containing buffers at pH 8.5 can be markedly modified using Cu(2+) instead of O2 as an oxidant: the deposition kinetics remains linear up to thicknesses of more than 70 nm, whereas the film growth stops at 45 ± 5 nm in the presence of 02. In addition, the films prepared from Cu(2+) containing solutions display an absorption spectrum with defined peaks at 320 and 370 nm, which are absent in the spectra of films prepared in oxygenated solutions. The replacement of Tris buffer by phosphate buffer also has a marked effect on the melanin deposition kinetics.

  7. Crossover from in-plane to perpendicular anisotropy in Pt/CoFe/AlOx sandwiches as a function of Al oxidation: A very accurate control of the oxidation of tunnel barriers

    NASA Astrophysics Data System (ADS)

    Monso, S.; Rodmacq, B.; Auffret, S.; Casali, G.; Fettar, F.; Gilles, B.; Dieny, B.; Boyer, P.

    2002-06-01

    By measuring the extraordinary Hall effect on a series of naturally oxidized Pt3 nm/Co90Fe10 0.6 nm/Al tAl samples with 0oxidation of Al at the CoFe/AlOx interface has a dramatic effect on the magnetic anisotropy of the transition-metal layer. These sharp crossovers of anisotropy provide a very accurate and convenient way to monitor the oxidation of the tunnel barrier in magnetic tunnel junctions. This technique is also applied to characterize the oxidation kinetics of various ultrathin metallic layers as well as the aging effect in alumina barriers.

  8. AGEs Promote Oxidative Stress and Induce Apoptosis in Retinal Pigmented Epithelium Cells RAGE-dependently.

    PubMed

    Wang, Xin-Ling; Yu, Tao; Yan, Qi-Chang; Wang, Wei; Meng, Nan; Li, Xue-Jiao; Luo, Ya-Hong

    2015-06-01

    Advanced glycation end products (AGEs) are extremely accumulated in diabetes mellitus, particularly in retinal vascular and epithelium cells, and are confirmed to contribute to diabetic retinopathy (DR). In the present study, we determined the promotion by AGEs to the oxidative stress and mitochondrial dysfunction in retinal pigmented epithelium ARPE-19 cells and investigated the influence by the knockdown or the overexpression of receptor for AGEs (RAGE) on the AGE-promoted oxidative stress and mitochondrial dysfunction. Furthermore, we determined the induction by AGEs to the cell apoptosis and to the activation of B-cell lymphoma 2 (Bcl-2) families in the AGE-BSA-induced apoptosis, and examined the RAGE-dependence in such induction. Results demonstrated that AGE-BSA upregulated the hydrogen peroxide production and induced mitochondrial dysfunction in ARPE-19 cells, dose-dependently. And the further investigation indicated that the AGE-RAGE interaction was required for the induction of oxidative stress and mitochondrial dysfunction. Moreover, the AGE-BSA treatment promoted a significantly high level of apoptotic cells, and the Bcl-2 family was implicated in the AGE-BSA-induced apoptosis, there was a significant high level of Cyt c release, Bcl-2-associated X protein (Bax) induction, Bcl-2 reduction, and caspase 9 activation in the AGE-BSA-treated cells. In conclusion, the present study recognized the apoptosis induction by AGE-BSAs in the retinal epithelium ARPE-19 cells, RAGE-dependently. The mitochondrial dysfunction was induced, and the Bcl-2 family was deregulated during the AGE-BSA-induced ARPE-19 cell apoptosis.

  9. Interface states in Al2O3/AlGaN/GaN metal-oxide-semiconductor structure by frequency dependent conductance technique

    NASA Astrophysics Data System (ADS)

    Liao, Xue-Yang; Zhang, Kai; Zeng, Chang; Zheng, Xue-Feng; En, Yun-Fei; Lai, Ping; Hao, Yue

    2014-05-01

    Frequency dependent conductance measurements are implemented to investigate the interface states in Al2O3/AlGaN/GaN metal-oxide-semiconductor (MOS) structures. Two types of device structures, namely, the recessed gate structure (RGS) and the normal gate structure (NGS), are studied in the experiment. Interface trap parameters including trap density Dit, trap time constant τit, and trap state energy ET in both devices have been determined. Furthermore, the obtained results demonstrate that the gate recess process can induce extra traps with shallower energy levels at the Al2O3/AlGaN interface due to the damage on the surface of the AlGaN barrier layer resulting from reactive ion etching (RIE).

  10. Concentration dependences of elastooptic coefficients of germanate glasses containing lead and bismuth oxides

    SciTech Connect

    Rabukhin, A.I.

    1995-11-01

    Concentration dependences of elastooptic coefficients of lead - bismuth - germanate glasses with compositions from virtually the entire range of glass formation in the system PbO-Bi{sub 2}O{sub 3}-GeO{sub 2} are investigated. Partial elastooptic coefficients of the oxide ingredients of the investigated glasses are determined. The results are interpreted with consideration of the nature of the elastooptic interaction in glasses subjected to uniaxial stress. The data can be used for designing compositions of optical media for the light and acoustic lines of acoustooptical devices.

  11. Dose dependence of interface traps in gate oxides at high levels of total dose

    SciTech Connect

    Baze, M.P.; Plaag, R.E.; Johnston, A.H. )

    1989-12-01

    Interface traps in gate oxides were found to saturate at high total dose levels. An empirical model was developed to describe the nonlinear dependence and saturation characteristics. Three different processes were studied including CMOS/SOS, hardened bulk CMOS and unhardened bulk CMOS using several combinations of dose rate and bias. An evaluation was made of the model's accuracy in extrapolating the effect of interface traps to very high doses. A possible application of the model in characterizing devices for space environments is discussed along with implications for a physical model of radiation induced interface trap buildup.

  12. Size-dependant heating rates of iron oxide nanoparticles for magnetic fluid hyperthermia.

    PubMed

    Gonzales-Weimuller, Marcela; Zeisberger, Matthias; Krishnan, Kannan M

    2009-07-01

    Using the thermal decomposition of organometallics method we have synthesized high-quality, iron oxide nanoparticles of tailorable size up to ~15nm and transferred them to a water phase by coating with a biocompatible polymer. The magnetic behavior of these particles was measured and fit to a log-normal distribution using the Chantrell method and their polydispersity was confirmed to be very narrow. By performing calorimetry measurements with these monodisperse particles we have unambiguously demonstrated, for the first time, that at a given frequency, heating rates of superparamagnetic particles are dependent on particle size, in agreement with earlier theoretical predictions.

  13. Plasmin-dependent modulation of the blood–brain barrier: a major consideration during tPA-induced thrombolysis?

    PubMed Central

    Niego, Be'eri; Medcalf, Robert L

    2014-01-01

    Plasmin, the principal downstream product of tissue-type plasminogen activator (tPA), is known for its potent fibrin-degrading capacity but is also recognized for many non-fibrinolytic activities. Curiously, plasmin has not been conclusively linked to blood–brain barrier (BBB) disruption during recombinant tPA (rtPA)-induced thrombolysis in ischemic stroke. This is surprising given the substantial involvement of tPA in the modulation of BBB permeability and the co-existence of tPA and plasminogen in both blood and brain throughout the ischemic event. Here, we review the work that argues a role for plasmin together with endogenous tPA or rtPA in BBB alteration, presenting the overall controversy around the topic yet creating a rational case for an involvement of plasmin in this process. PMID:24896566

  14. Dependency of temperature on polarization in CH4/N2 dielectric barrier discharge plasma: A crude assumption

    NASA Astrophysics Data System (ADS)

    Majumdar, Abhijit; Ghosh, Basudev; Hippler, Rainer

    2010-11-01

    We have investigated the variations of polarization (P) and the temperature (ΔT) at the electrode surfaces during the deposition of C-N layer in CH4/N2 (1:2) dielectric barrier discharge plasma. The reactive deposition process influences the surface temperature, polarization, and the value of the in situ dielectric constant. We have developed a crude model that correlates the surface temperature and surface polarization with thin film properties. We assume that during the thin film deposition process, the atomic mean kinetic energy is equal to the electrostatic energy stored in the electrode surface area. Theoretically estimated temperature is found to agree well with the experimental results. However, the linear model thus developed cannot be used to explain the phenomena in the interfacial polarization stage that requires a nonlinear theory.

  15. Ceruloplasmin enhances smooth muscle cell- and endothelial cell-mediated low density lipoprotein oxidation by a superoxide-dependent mechanism

    NASA Technical Reports Server (NTRS)

    Mukhopadhyay, C. K.; Ehrenwald, E.; Fox, P. L.

    1996-01-01

    Cultured vascular smooth muscle cells (SMC) and endothelial cells (EC) stimulate low density lipoprotein (LDL) oxidation by free radical-mediated, transition metal-dependent mechanisms. The physiological source(s) of metal ions is not known; however, purified ceruloplasmin, a plasma protein containing 7 coppers, oxidizes LDL in vitro. We now show that ceruloplasmin also increases LDL oxidation by vascular cells. In metal ion-free medium, human ceruloplasmin increased bovine aortic SMC- and EC-mediated LDL oxidation by up to 30- and 15-fold, respectively. The maximal response was at 100-300 microg ceruloplasmin/ml, a level at or below the unevoked physiological plasma concentration. Oxidant activity was dependent on protein structure as a specific proteolytic cleavage or removal of one of the seven ceruloplasmin copper atoms inhibited activity. Three lines of evidence indicated a critical role for cellular superoxide (O2.) in ceruloplasmin-stimulated oxidation. First, the rate of production of O2. by cells correlated with their rates of LDL oxidation. Second, superoxide dismutase effectively blocked ceruloplasmin-stimulated oxidation by both cell types. Finally, O2. production by SMC quantitatively accounted for the observed rate of LDL oxidation. To show this, the course of O2. production by SMC was simulated by repeated addition of xanthine and xanthine oxidase to culture medium under cell-free conditions. Neither ceruloplasmin nor O2. alone increased LDL oxidation, but together they completely reconstituted the oxidation rate of ceruloplasmin-stimulated SMC. These results are the first to show that ceruloplasmin stimulates EC- and SMC-mediated oxidation of LDL and that cell-derived O2. accounts quantitatively for metal-dependent, free radical-initiated oxidation of LDL by these cells.

  16. Gate Oxide Reliability Characterization of Tungsten Polymetal Gate with Low-Contact-Resistive WSix/WN Diffusion Barrier in Memory Devices

    NASA Astrophysics Data System (ADS)

    Sung, Min Gyu; Lim, Kwan-Yong; Cho, Heung-Jae; Lee, Seung Ryong; Jang, Se-Aug; Kim, Yong Soo; Kim, Tae-Yoon; Yang, Hong-Seon; Ku, Ja-Chun; Kim, Jin Woong

    2007-11-01

    Gate oxide reliability characteristics using different diffusion barrier metals for a tungsten polycrystalline silicon (poly-Si) gate stack were investigated in detail. The insertion of a thin WSix layer in a tungsten poly gate stack could effectively relieve the mechanical stress of a gate hardmask nitride film during a post thermal process, which contributes to better gate oxide reliability and the stress-immunity of the transistor. This insertion could also prevent the formation of a Si-N inter-dielectric layer, which could lower the contact resistance between poly and tungsten effectively. A W/WN/WSix/poly gate stack could be a promising candidate for a future W poly gate that shows reliable high-speed characteristics in dynamic random access memory applications.

  17. The Dependence of the Oxidation Enhancement of InP(100) Surface on the Coverage of the Adsorbed Cs

    SciTech Connect

    Sun, Yun

    2010-06-07

    We report the oxidation of the InP(100) surface promoted by adsorbed Cs by synchrotron radiation photoemission. Oxygen exposure causes reduction of the charge transferred to the InP substrate from Cs and the growth of indium oxide and phosphorous oxide. The oxide growth displays a clear dependence on the Cs coverage. The oxidation of phosphorous is negligible up to 1000 L of O{sub 2} exposure when the Cs coverage is less than half a monolayer (ML), but the formation of the second half monolayer of Cs greatly accelerates the oxidation. This different enhancement of the InP oxidation by the first and the second half monolayer of Cs is due to the double layer structure of the adsorbed Cs atoms, and consequently the higher 6s electron density in the Cs atoms when Cs coverage is larger than 0.5 ML.

  18. Cyclic AMP-dependent phosphorylation of neuronal nitric oxide synthase mediates penile erection.

    PubMed

    Hurt, K Joseph; Sezen, Sena F; Lagoda, Gwen F; Musicki, Biljana; Rameau, Gerald A; Snyder, Solomon H; Burnett, Arthur L

    2012-10-09

    Nitric oxide (NO) generated by neuronal NO synthase (nNOS) initiates penile erection, but has not been thought to participate in the sustained erection required for normal sexual performance. We now show that cAMP-dependent phosphorylation of nNOS mediates erectile physiology, including sustained erection. nNOS is phosphorylated by cAMP-dependent protein kinase (PKA) at serine(S)1412. Electrical stimulation of the penile innervation increases S1412 phosphorylation that is blocked by PKA inhibitors but not by PI3-kinase/Akt inhibitors. Stimulation of cAMP formation by forskolin also activates nNOS phosphorylation. Sustained penile erection elicited by either intracavernous forskolin injection, or augmented by forskolin during cavernous nerve electrical stimulation, is prevented by the NOS inhibitor L-NAME or in nNOS-deleted mice. Thus, nNOS mediates both initiation and maintenance of penile erection, implying unique approaches for treating erectile dysfunction.

  19. The position dependent 15N enrichment of nitrous oxide in the stratosphere.

    PubMed

    Röckmann, T; Kaiser, J; Brenninkmeijer, C A; Brand, W A; Borchers, R; Crowley, J N; Wollenhaupt, M; Crutzen, P J

    2001-01-01

    The position dependent 15N fractionation of nitrous oxide (N2O), which cannot be obtained from mass spectrometric analysis on molecular N2O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO+ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent 15N fractionations occur in the photolysis of N2O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N2O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for 15N14NO and 14N15NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N2O with O(1D).

  20. Diesel exhaust particles induce oxidative stress, proinflammatory signaling, and P-glycoprotein up-regulation at the blood-brain barrier.

    PubMed

    Hartz, Anika M S; Bauer, Björn; Block, Michelle L; Hong, Jau-Shyong; Miller, David S

    2008-08-01

    Here, we report that diesel exhaust particles (DEPs), a major constituent of urban air pollution, affect blood-brain barrier function at the tissue, cellular, and molecular levels. Isolated rat brain capillaries exposed to DEPs showed increased expression and transport activity of the key drug efflux transporter, P-glycoprotein (6 h EC(50) was approximately 5 microg/ml). Up-regulation of P-glycoprotein was abolished by blocking transcription or protein synthesis. Inhibition of NADPH oxidase or pretreatment of capillaries with radical scavengers ameliorated DEP-induced P-glycoprotein up-regulation, indicating a role for reactive oxygen species in signaling. DEP exposure also increased brain capillary tumor necrosis factor-alpha (TNF-alpha) levels. DEP-induced P-glycoprotein up-regulation was abolished when TNF-receptor 1 (TNF-R1) was blocked and was not evident in experiments with capillaries from TNF-R1 knockout mice. Inhibition of JNK, but not NF-kappaB, blocked DEP-induced P-glycoprotein up-regulation, indicating a role for AP-1 in the signaling pathway. Consistent with this, DEPs increased phosphorylation of c-jun. Together, our results show for the first time that a component of air pollution, DEPs, alters blood-brain barrier function through oxidative stress and proinflammatory cytokine production. These experiments disclose a novel blood-brain barrier signaling pathway, with clear implications for environmental toxicology, CNS pathology, and the pharmacotherapy of CNS disorders.

  1. Multi-scale analysis of the diffusion barrier layer of gadolinia-doped ceria in a solid oxide fuel cell operated in a stack for 3000 h

    NASA Astrophysics Data System (ADS)

    Morales, M.; Miguel-Pérez, V.; Tarancón, A.; Slodczyk, A.; Torrell, M.; Ballesteros, B.; Ouweltjes, J. P.; Bassat, J. M.; Montinaro, D.; Morata, A.

    2017-03-01

    The state-of-the-art materials for SOFCs are yttria-stabilized zirconia as electrolyte and lanthanum strontium cobalt ferrite as cathode. However, the formation of insulating phases between them requires the use of diffusion barriers, typically made of gadolinia doped ceria. The study of the stability of this layer during the fabrication and in operando is currently one of the major goals of the SOFC industry. In this work, the cation inter-diffusion at the cathode/barrier layer/electrolyte region is analysed for an anode-supported cell industrially fabricated by conventional techniques, assembled in a short-stack and tested under real operation conditions for 3000 h. A comprehensive study of this cell, and an equivalent non-operated one, is performed in order to understand the inter-diffusion mechanisms with possible effects on the final performance. The analyses evidence that the cation diffusion is occurring during the fabrication process. Despite the significant diffusion of Ce,Gd, Zr, Y and Sr cations, the formation of typically reported CGO-YSZ solid solution is not observed while the presence of isolated grains of SrZrO3 is proved. All in all, this study presents new insights into the stability of the typically employed diffusion barriers for solid oxide cells that will guide future strategies to improve their performance and durability.

  2. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    PubMed Central

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-01-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments. PMID:27492680

  3. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    NASA Astrophysics Data System (ADS)

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-08-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments.

  4. Oxidized Phospholipids Inhibit the Formation of Cholesterol-Dependent Plasma Membrane Nanoplatforms

    PubMed Central

    Brameshuber, Mario; Sevcsik, Eva; Rossboth, Benedikt K.; Manner, Christina; Deigner, Hans-Peter; Peksel, Begüm; Péter, Mária; Török, Zsolt; Hermetter, Albin; Schütz, Gerhard J.

    2016-01-01

    We previously developed a single-molecule microscopy method termed TOCCSL (thinning out clusters while conserving stoichiometry of labeling), which allows for direct imaging of stable nanoscopic platforms with raft-like properties diffusing in the plasma membrane. As a consensus raft marker, we chose monomeric GFP linked via a glycosylphosphatidylinositol (GPI) anchor to the cell membrane (mGFP-GPI). With this probe, we previously observed cholesterol-dependent homo-association to nanoplatforms diffusing in the plasma membrane of live CHO cells. Here, we report the release of this homo-association upon addition of 1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphocholine (POVPC) or 1-palmitoyl-2-glutaroyl-sn-glycero-3-phosphocholine, two oxidized phospholipids (oxPLs) that are typically present in oxidatively modified low-density lipoprotein. We found a dose-response relationship for mGFP-GPI nanoplatform disintegration upon addition of POVPC, correlating with the signal of the apoptosis marker Annexin V-Cy3. Similar concentrations of lysolipid showed no effect, indicating that the observed phenomena were not linked to properties of the lipid bilayer itself. Inhibition of acid sphingomyelinase by NB-19 before addition of POVPC completely abolished nanoplatform disintegration by oxPLs. In conclusion, we were able to determine how oxidized lipid species disrupt mGFP-GPI nanoplatforms in the plasma membrane. Our results favor an indirect mechanism involving acid sphingomyelinase activity rather than a direct interaction of oxPLs with nanoplatform constituents. PMID:26745423

  5. Microbiology, ecology, and application of the nitrite-dependent anaerobic methane oxidation process

    PubMed Central

    Shen, Li-Dong; He, Zhan-Fei; Zhu, Qun; Chen, Dong-Qing; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping; Hu, Bao-Lan

    2012-01-01

    Nitrite-dependent anaerobic methane oxidation (n-damo), which couples the anaerobic oxidation of methane to denitrification, is a recently discovered process mediated by “Candidatus Methylomirabilis oxyfera.” M. oxyfera is affiliated with the “NC10” phylum, a phylum having no members in pure culture. Based on the isotopic labeling experiments, it is hypothesized that M. oxyfera has an unusual intra-aerobic pathway for the production of oxygen via the dismutation of nitric oxide into dinitrogen gas and oxygen. In addition, the bacterial species has a unique ultrastructure that is distinct from that of other previously described microorganisms. M. oxyfera-like sequences have been recovered from different natural habitats, suggesting that the n-damo process potentially contributes to global carbon and nitrogen cycles. The n-damo process is a process that can reduce the greenhouse effect, as methane is more effective in heat-trapping than carbon dioxide. The n-damo process, which uses methane instead of organic matter to drive denitrification, is also an economical nitrogen removal process because methane is a relatively inexpensive electron donor. This mini-review summarizes the peculiar microbiology of M. oxyfera and discusses the potential ecological importance and engineering application of the n-damo process. PMID:22905032

  6. Microbiology, ecology, and application of the nitrite-dependent anaerobic methane oxidation process.

    PubMed

    Shen, Li-Dong; He, Zhan-Fei; Zhu, Qun; Chen, Dong-Qing; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping; Hu, Bao-Lan

    2012-01-01

    Nitrite-dependent anaerobic methane oxidation (n-damo), which couples the anaerobic oxidation of methane to denitrification, is a recently discovered process mediated by "Candidatus Methylomirabilis oxyfera." M. oxyfera is affiliated with the "NC10" phylum, a phylum having no members in pure culture. Based on the isotopic labeling experiments, it is hypothesized that M. oxyfera has an unusual intra-aerobic pathway for the production of oxygen via the dismutation of nitric oxide into dinitrogen gas and oxygen. In addition, the bacterial species has a unique ultrastructure that is distinct from that of other previously described microorganisms. M. oxyfera-like sequences have been recovered from different natural habitats, suggesting that the n-damo process potentially contributes to global carbon and nitrogen cycles. The n-damo process is a process that can reduce the greenhouse effect, as methane is more effective in heat-trapping than carbon dioxide. The n-damo process, which uses methane instead of organic matter to drive denitrification, is also an economical nitrogen removal process because methane is a relatively inexpensive electron donor. This mini-review summarizes the peculiar microbiology of M. oxyfera and discusses the potential ecological importance and engineering application of the n-damo process.

  7. Myeloperoxidase-dependent lipid peroxidation promotes the oxidative modification of cytosolic proteins in phagocytic neutrophils.

    PubMed

    Wilkie-Grantham, Rachel P; Magon, Nicholas J; Harwood, D Tim; Kettle, Anthony J; Vissers, Margreet C; Winterbourn, Christine C; Hampton, Mark B

    2015-04-10

    Phagocytic neutrophils generate reactive oxygen species to kill microbes. Oxidant generation occurs within an intracellular phagosome, but diffusible species can react with the neutrophil and surrounding tissue. To investigate the extent of oxidative modification, we assessed the carbonylation of cytosolic proteins in phagocytic neutrophils. A 4-fold increase in protein carbonylation was measured within 15 min of initiating phagocytosis. Carbonylation was dependent on NADPH oxidase and myeloperoxidase activity and was inhibited by butylated hydroxytoluene and Trolox, indicating a role for myeloperoxidase-dependent lipid peroxidation. Proteomic analysis of target proteins revealed significant carbonylation of the S100A9 subunit of calprotectin, a truncated form of Hsp70, actin, and hemoglobin from contaminating erythrocytes. The addition of the reactive aldehyde 4-hydroxynonenal (HNE) caused carbonylation, and HNE-glutathione adducts were detected in the cytosol of phagocytic neutrophils. The post-translational modification of neutrophil proteins will influence the functioning and fate of these immune cells in the period following phagocytic activation, and provides a marker of neutrophil activation during infection and inflammation.

  8. Diversity and enrichment of nitrite-dependent anaerobic methane oxidizing bacteria from wastewater sludge.

    PubMed

    Luesken, Francisca A; van Alen, Theo A; van der Biezen, Erwin; Frijters, Carla; Toonen, Ger; Kampman, Christel; Hendrickx, Tim L G; Zeeman, Grietje; Temmink, Hardy; Strous, Marc; Op den Camp, Huub J M; Jetten, Mike S M

    2011-11-01

    Recently discovered microorganisms affiliated to the bacterial phylum NC10, named "Candidatus Methylomirabilis oxyfera", perform nitrite-dependent anaerobic methane oxidation. These microorganisms could be important players in a novel way of anaerobic wastewater treatment where ammonium and residual dissolved methane might be removed at the expense of nitrate or nitrite. To find suitable inocula for reactor startup, ten selected wastewater treatment plants (WWTPs) located in The Netherlands were screened for the endogenous presence of M. oxyfera using molecular diagnostic methods. We could identify NC10 bacteria with 98% similarity to M. oxyfera in nine out of ten WWTPs tested. Sludge from one selected WWTP was used to start a new enrichment culture of NC10 bacteria. This enrichment was monitored using specific pmoA primers and M. oxyfera cells were visualized with fluorescence oligonucleotide probes. After 112 days, the enrichment consumed up to 0.4 mM NO(2)(-) per day. The results of this study show that appropriate sources of biomass, enrichment strategies, and diagnostic tools existed to start and monitor pilot scale tests for the implementation of nitrite-dependent methane oxidation in wastewater treatment at ambient temperature.

  9. Myeloperoxidase-dependent Lipid Peroxidation Promotes the Oxidative Modification of Cytosolic Proteins in Phagocytic Neutrophils*

    PubMed Central

    Wilkie-Grantham, Rachel P.; Magon, Nicholas J.; Harwood, D. Tim; Kettle, Anthony J.; Vissers, Margreet C.; Winterbourn, Christine C.; Hampton, Mark B.

    2015-01-01

    Phagocytic neutrophils generate reactive oxygen species to kill microbes. Oxidant generation occurs within an intracellular phagosome, but diffusible species can react with the neutrophil and surrounding tissue. To investigate the extent of oxidative modification, we assessed the carbonylation of cytosolic proteins in phagocytic neutrophils. A 4-fold increase in protein carbonylation was measured within 15 min of initiating phagocytosis. Carbonylation was dependent on NADPH oxidase and myeloperoxidase activity and was inhibited by butylated hydroxytoluene and Trolox, indicating a role for myeloperoxidase-dependent lipid peroxidation. Proteomic analysis of target proteins revealed significant carbonylation of the S100A9 subunit of calprotectin, a truncated form of Hsp70, actin, and hemoglobin from contaminating erythrocytes. The addition of the reactive aldehyde 4-hydroxynonenal (HNE) caused carbonylation, and HNE-glutathione adducts were detected in the cytosol of phagocytic neutrophils. The post-translational modification of neutrophil proteins will influence the functioning and fate of these immune cells in the period following phagocytic activation, and provides a marker of neutrophil activation during infection and inflammation. PMID:25697357

  10. Flow-dependent regulation of endothelial nitric oxide synthase: role of protein kinases

    NASA Technical Reports Server (NTRS)

    Boo, Yong Chool; Jo, Hanjoong

    2003-01-01

    Vascular endothelial cells are directly and continuously exposed to fluid shear stress generated by blood flow. Shear stress regulates endothelial structure and function by controlling expression of mechanosensitive genes and production of vasoactive factors such as nitric oxide (NO). Though it is well known that shear stress stimulates NO production from endothelial nitric oxide synthase (eNOS), the underlying molecular mechanisms remain unclear and controversial. Shear-induced production of NO involves Ca2+/calmodulin-independent mechanisms, including phosphorylation of eNOS at several sites and its interaction with other proteins, including caveolin and heat shock protein-90. There have been conflicting results as to which protein kinases-protein kinase A, protein kinase B (Akt), other Ser/Thr protein kinases, or tyrosine kinases-are responsible for shear-dependent eNOS regulation. The functional significance of each phosphorylation site is still unclear. We have attempted to summarize the current status of understanding in shear-dependent eNOS regulation.

  11. Diacylglycerol kinases activate tobacco NADPH oxidase-dependent oxidative burst in response to cryptogein.

    PubMed

    Cacas, Jean-Luc; Gerbeau-Pissot, Patricia; Fromentin, Jérôme; Cantrel, Catherine; Thomas, Dominique; Jeannette, Emmanuelle; Kalachova, Tetiana; Mongrand, Sébastien; Simon-Plas, Françoise; Ruelland, Eric

    2017-04-01

    Cryptogein is a 10 kDa protein secreted by the oomycete Phytophthora cryptogea that activates defence mechanisms in tobacco plants. Among early signalling events triggered by this microbial-associated molecular pattern is a transient apoplastic oxidative burst which is dependent on the nicotinamide adenine dinucleotide phosphate (NADPH) oxidase activity of the RESPIRATORY BURST OXIDASE HOMOLOG isoform D (RBOHD). Using radioactive [(33) P]-orthophosphate labelling of tobacco Bright Yellow-2 suspension cells, we here provide in vivo evidence for a rapid accumulation of phosphatidic acid (PA) in response to cryptogein because of the coordinated onset of phosphoinositide-dependent phospholipase C and diacylglycerol kinase (DGK) activities. Both enzyme specific inhibitors and silencing of the phylogenetic cluster III of the tobacco DGK family were found to reduce PA production upon elicitation and to strongly decrease the RBOHD-mediated oxidative burst. Therefore, it appears that PA originating from DGK controls NADPH-oxidase activity. Amongst cluster III DGKs, the expression of DGK5-like was up-regulated in response to cryptogein. Besides DGK5-like is likely to be the main cluster III DGK isoform silenced in one of our mutant lines, making it a strong candidate for the observed response to cryptogein. The relevance of these results is discussed with regard to early signalling lipid-mediated events in plant immunity.

  12. Size-dependent cytotoxicity and inflammatory responses of PEGylated silica-iron oxide nanocomposite size series

    NASA Astrophysics Data System (ADS)

    Injumpa, Wishulada; Ritprajak, Patcharee; Insin, Numpon

    2017-04-01

    Iron oxides nanoparticles have been utilized in biological systems and biomedical applications for many years because they are relatively safe and stable comparing to other magnetic nanomaterials. In some applications, iron oxide nanoparticles were modified with silica in order to be more stable in biological systems and able to be functionalized with various functional groups. Moreover, poly(ethylene glycol) (PEG) was one on the most used polymer to graft onto the nanoparticles in order to increase their biocompatibility, dispersibility and stability in aqueous solutions. Therefore, the nanocomposites comprising iron oxide nanoparticles, silica, and PEG could become multifunctional carriers combining superparamagnetic character, multi-functionality and high stability in biological environments. Herein, we reported the preparation of the nanocomposites and effects of their sizes on cytotoxicity and inflammatory responses. The PEGylated silica-iron oxide nanocomposites were prepared by coating of poly(poly(ethylene glycol) monomethyl ether methacrylate) (PPEGMA) on magnetic nanoparticle-silica nanocomposites via Atom Transfer Radical Polymerization (ATRP). The iron oxide nanoparticles were synthesized using a thermal decomposition method. The silica shells were then coated on iron oxides nanoparticles using reverse microemulsion and sol-gel methods. The size series of the nanocomposites with the diameter of 24.86±4.38, 45.24±5.00, 98.10±8.88 and 202.22±6.70 nm as measured using TEM were obtained. Thermogravimetric analysis (TGA) was used for the determination of % weight of PPEGMA on the nanocomposites showing the weight loss of ranging from 65% for smallest particles to 30% for largest particles. The various sizes (20, 40, 100, 200 nm) and concentrations (10, 100, 1000 μg/mL) of the nanocomposites were tested for their cytotoxicity in fibroblast and macrophage cell lines using MTT assay. The different sizes did not affect cell viability of fibroblast, albeit

  13. Induction of calcium-dependent nitric oxide synthases by sex hormones.

    PubMed Central

    Weiner, C P; Lizasoain, I; Baylis, S A; Knowles, R G; Charles, I G; Moncada, S

    1994-01-01

    We have examined the effects of pregnancy and sex hormones on calcium-dependent and calcium-independent nitric oxide synthases (NOSs) in the guinea pig. Pregnancy (near term) caused a > 4-fold increase in the activity of calcium-dependent NOS in the uterine artery and at least a doubling in the heart, kidney, skeletal muscle, esophagus, and cerebellum. The increase in NOS activity in the cerebellum during pregnancy was inhibited by the estrogen-receptor antagonist tamoxifen. Treatment with estradiol (but not progesterone) also increased calcium-dependent NOS activity in the tissues examined from both females and males. Testosterone increased calcium-dependent NOS only in the cerebellum. No significant change in calcium-independent NOS activity was observed either during pregnancy or after the administration of any sex hormone. Both pregnancy and estradiol treatment increased the amount of mRNAs for NOS isozymes eNOS and nNOS in skeletal muscle, suggesting that the increases in NOS activity result from enzyme induction. Thus both eNOS and nNOS are subject to regulation by estrogen, an action that could explain some of the changes that occur during pregnancy and some gender differences in physiology and pathophysiology. Images PMID:7515189

  14. Dietary restriction involves NAD⁺ -dependent mechanisms and a shift toward oxidative metabolism.

    PubMed

    Moroz, Natalie; Carmona, Juan J; Anderson, Edward; Hart, Anne C; Sinclair, David A; Blackwell, T Keith

    2014-12-01

    Interventions that slow aging and prevent chronic disease may come from an understanding of how dietary restriction (DR) increases lifespan. Mechanisms proposed to mediate DR longevity include reduced mTOR signaling, activation of the NAD⁺ -dependent deacylases known as sirtuins, and increases in NAD⁺ that derive from higher levels of respiration. Here, we explored these hypotheses in Caenorhabditis elegans using a new liquid feeding protocol. DR lifespan extension depended upon a group of regulators that are involved in stress responses and mTOR signaling, and have been implicated in DR by some other regimens [DAF-16 (FOXO), SKN-1 (Nrf1/2/3), PHA-4 (FOXA), AAK-2 (AMPK)]. Complete DR lifespan extension required the sirtuin SIR-2.1 (SIRT1), the involvement of which in DR has been debated. The nicotinamidase PNC-1, a key NAD⁺ salvage pathway component, was largely required for DR to increase lifespan but not two healthspan indicators: movement and stress resistance. Independently of pnc-1, DR increased the proportion of respiration that is coupled to ATP production but, surprisingly, reduced overall oxygen consumption. We conclude that stress response and NAD⁺ -dependent mechanisms are each critical for DR lifespan extension, although some healthspan benefits do not require NAD⁺ salvage. Under DR conditions, NAD⁺ -dependent processes may be supported by a DR-induced shift toward oxidative metabolism rather than an increase in total respiration.

  15. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  16. Estimating the extent of surface oxidation by measuring the porosity dependent dielectrics of oxygenated porous silicon [rapid communication

    NASA Astrophysics Data System (ADS)

    Pan, L. K.; Sun, Chang Q.; Li, C. M.

    2005-02-01

    Surface oxidation and porosity variation play significant roles in the dielectric performance of porous silicon (PS) yet discriminating the contribution of these events is a challenge. Here we present an analytical solution that covers contributions from the components of silicon oxide surface, silicon backbone and voids using a serial-parallel capacitance structure. Agreement between modeling predictions and measurement has been realized, which turns out an effective method that enables us to estimate the extent of surface oxidation of a specimen by measuring the porosity dependent dielectric response of the chemically passivated PS, and provides guidelines that could be useful for designing dielectric porous structures with surface oxidation.

  17. Dependence of Ozone Generation on Gas Temperature Distribution in AC Atmospheric Pressure Dielectric Barrier Discharge in Oxygen

    NASA Astrophysics Data System (ADS)

    Takahashi, Go; Akashi, Haruaki

    AC atmospheric pressure multi-filament dielectric barrier discharge in oxygen has been simulated using two dimensional fluid model. In the discharge, three kinds of streamers have been obtained. They are primary streamers, small scale streamers and secondary streamers. The primary streamers are main streamers in the discharge and the small scale streamers are formed after the ceasing of the primary streamers. And the secondary streamers are formed on the trace of the primary streamers. In these streamers, the primary and the small scale streamers are very effective to generate O(3P) oxygen atoms which are precursor of ozone. And the ozone is generated mainly in the vicinity of the dielectrics. In high gas temperature region, ozone generation decreases in general. However, increase of the O(3P) oxygen atom density in high gas temperature region compensates decrease of ozone generation rate coefficient. As a result, amount of ozone generation has not changed. But if the effect of gas temperature was neglected, amount of ozone generation increases 10%.

  18. GPHR-dependent functions of the Golgi apparatus are essential for the formation of lamellar granules and the skin barrier.

    PubMed

    Tarutani, Masahito; Nakajima, Kimiko; Uchida, Yoshikazu; Takaishi, Mikiro; Goto-Inoue, Naoko; Ikawa, Masahito; Setou, Mitsutoshi; Kinoshita, Taroh; Elias, Peter M; Sano, Shigetoshi; Maeda, Yusuke

    2012-08-01

    The lumen of the Golgi apparatus is regulated to be weakly acidic, which is critical for its functions. The Golgi pH regulator (GPHR) is an anion channel essential for normal acidification of the Golgi apparatus, and is therefore required for its functions. The Golgi apparatus has been thought to be the origin of lamellar granules in the skin. To study the functional role(s) of GPHR in the skin, we established keratinocyte-specific GPHR-knockout mice using the Cre-loxP system. These mutant mice exhibited hypopigmented skin, hair loss, and scaliness. Histological examination of GPHR-knockout mice showed ballooning of the basal cells and follicular dysplasia. In addition, inflammatory cells were seen in the dermis. The expression of trans-Golgi network 46, a marker for lamellar bodies, and kallikrein 7, a protein within lamellar bodies, is diminished in GPHR-knockout mouse skin. Examination by electron microscopy revealed that keratinocytes produced aberrant lamellar bodies. The transepidermal water loss of these knockout mice was increased compared with wild-type mice. Moreover, expression of cathelicidin-related antimicrobial peptide (CRAMP) in the skin was diminished. These results suggest that GPHR is essential for the homeostasis of the epidermis including the formation of lamellar bodies and for the barrier function.

  19. Oxidative stress stimulates skeletal muscle glucose uptake through a phosphatidylinositol 3-kinase-dependent pathway

    PubMed Central

    Higaki, Yasuki; Mikami, Toshio; Fujii, Nobuharu; Hirshman, Michael F.; Koyama, Katsuhiro; Seino, Tetsuya; Tanaka, Keitaro; Goodyear, Laurie J.

    2010-01-01

    We determined the acute effects of oxidative stress on glucose uptake and intracellular signaling in skeletal muscle by incubating muscles with reactive oxygen species (ROS). Xanthine oxidase (XO) is a superoxide-generating enzyme that increases ROS. Exposure of isolated rat extensor digitorum longus (EDL) muscles to Hx/XO (Hx/XO) for 20 min resulted in a dose-dependent increase in glucose uptake. To determine whether the mechanism leading to Hx/XO-stimulated glucose uptake is associated with the production of H2O2, EDL muscles from rats were preincubated with the H2O2 scavenger catalase or the superoxide scavenger superoxide dismutase (SOD) prior to incubation with Hx/XO. Catalase treatment, but not SOD, completely inhibited the increase in Hx/XO-stimulated 2-deoxyglucose (2-DG) uptake, suggesting that H2O2 is an intermediary leading to Hx/XO-stimulated glucose uptake with incubation. Direct H2O2 also resulted in a dose-dependent increase in 2-DG uptake in isolated EDL muscles, and the maximal increase was threefold over basal levels at a concentration of 600 μmol/l H2O2. H2O2-stimulated 2-DG uptake was completely inhibited by the phosphatidylinositol 3-kinase (PI3K) inhibitor wortmannin, but not the nitric oxide inhibitor NG-monomethyl-L-arginine. H2O2 stimulated the phosphorylation of Akt Ser473 (7-fold) and Thr308 (2-fold) in isolated EDL muscles. H2O2 at 600 μmol/l had no effect on ATP concentrations and did not increase the activities of either the α1 or α2 catalytic isoforms of AMP-activated protein kinase. These results demonstrate that acute exposure of muscle to ROS is a potent stimulator of skeletal muscle glucose uptake and that this occurs through a PI3K-dependent mechanism. PMID:18303121

  20. Multilayer thermal barrier coating systems

    DOEpatents

    Vance, Steven J.; Goedjen, John G.; Sabol, Stephen M.; Sloan, Kelly M.

    2000-01-01

    The present invention generally describes multilayer thermal barrier coating systems and methods of making the multilayer thermal barrier coating systems. The thermal barrier coating systems comprise a first ceramic layer, a second ceramic layer, a thermally grown oxide layer, a metallic bond coating layer and a substrate. The thermal barrier coating systems have improved high temperature thermal and chemical stability for use in gas turbine applications.

  1. Genome-Enabled Studies of Anaerobic, Nitrate-Dependent Iron Oxidation in the Chemolithoautotrophic Bacterium Thiobacillus denitrificans

    NASA Astrophysics Data System (ADS)

    Beller, H. R.; Zhou, P.; Legler, T. C.; Chakicherla, A.; O'Day, P. A.

    2013-12-01

    Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV) oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II) oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II)-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II) oxidation, namely (a) whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV) oxides as electron donors under denitrifying conditions], (b) Fe(II) oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c) random transposon-mutagenesis studies with screening for Fe(II) oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II) oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III), which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II) oxidation and to current concepts of reverse electron transfer. Of the transposon mutants defective in Fe(II) oxidation, one mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I) was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II) oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV) oxidation, nor have other c-type cytochromes yet been implicated in the process.

  2. Oxidation-state dependence of rheology in peralkaline glasses of phonolitic composition

    NASA Astrophysics Data System (ADS)

    Scherrer, M. C.; Hess, K.-U.; Fehr, K. T.; Dingwell, D. B.

    2012-04-01

    The precise description of magmatic melts rheology at the glass transition is crucial in understanding dynamic processes in volcanology. The glass transition has been described to scale with the viscosity of the material according to Maxwell's relaxation theory for viscoelastic liquids (Dingwell and Webb, 1989). The temperature dependence of the viscosity of multi-component systems can adequately be calculated using empirical models such as Hess et al. (1996), Giordano et al. (2008) and Hui and Zhang (2008); yet, within these calculations, the influence of oxidation state has been so far considered minor and was consequently neglected. The rheological behavior of some iron-rich silicate melts has shown noteworthy oxidation state-dependent variations (Cukierman and Uhlmann 1974, Dingwell and Virgo 1987). The focus of our study is to improve the viscosity models by investigating the necessity of an additional redox-parameter. Thirteen re-melted glass samples of natural phonolitic composition (peralkaline lavas with 8.5 wt. % FeOtot) were produced under different oxygen fugacity (fO2) conditions in a CO/CO2 gas-mixing furnace. Their oxidation-state (Fe3+/Fetot) ranges from 0.44 to 0.93 (±0.05). The viscosity above the liquidus was recorded via the concentric cylinder technique at a constant temperature of 1186 ° C. Additionally, viscosities were measured in the interval of 107to 1011Pa swith temperatures up to 900 ° C at ambient pressure via a BAEHR micro-penetration viscometer. Glass transition temperatures (Tg) have been determined with a constant heating/cooling rate of 10K/min on a SETARAM Sensys evo DSC using the peak of the specific heat capacity curve. Under a constant temperature in the super-liquidus state, the viscosity increases strongly with increasing fO2. In the sub-liquidus state, the measured calorimetric Tgis shifted to lower temperatures as the ratio of ferrous/total iron decreases from 638 ° C to 610 ° C. However, there is no equivalent

  3. Barriers to transport in aperiodically time-dependent two-dimensional velocity fields: Nekhoroshev's theorem and "Nearly Invariant" tori

    NASA Astrophysics Data System (ADS)

    Wiggins, S.; Mancho, A. M.

    2014-02-01

    In this paper we consider fluid transport in two-dimensional flows from the dynamical systems point of view, with the focus on elliptic behaviour and aperiodic and finite time dependence. We give an overview of previous work on general nonautonomous and finite time vector fields with the purpose of bringing to the attention of those working on fluid transport from the dynamical systems point of view a body of work that is extremely relevant, but appears not to be so well known. We then focus on the Kolmogorov-Arnold-Moser (KAM) theorem and the Nekhoroshev theorem. While there is no finite time or aperiodically time-dependent version of the KAM theorem, the Nekhoroshev theorem, by its very nature, is a finite time result, but for a "very long" (i.e. exponentially long with respect to the size of the perturbation) time interval and provides a rigorous quantification of "nearly invariant tori" over this very long timescale. We discuss an aperiodically time-dependent version of the Nekhoroshev theorem due to Giorgilli and Zehnder (1992) (recently refined by Bounemoura, 2013 and Fortunati and Wiggins, 2013) which is directly relevant to fluid transport problems. We give a detailed discussion of issues associated with the applicability of the KAM and Nekhoroshev theorems in specific flows. Finally, we consider a specific example of an aperiodically time-dependent flow where we show that the results of the Nekhoroshev theorem hold.

  4. Temperature-dependent fatigue behaviors of ferroelectric ABO3-type and layered perovskite oxide thin films

    NASA Astrophysics Data System (ADS)

    Yuan, G. L.; Liu, J.-M.; Wang, Y. P.; Wu, D.; Zhang, S. T.; Shao, Q. Y.; Liu, Z. G.

    2004-04-01

    The temperature-dependent dielectric and ferroelectric fatigue behaviors of ABO3-type perovskite thin films Pb(Zr0.52Ti0.48)O3 (PZT) and Pb0.75La0.25TiO3 (PLT) and layered Aurivillius thin films SrBi2Ta2O9 (SBT) and Bi3.25La0.75Ti3O12 (BLT) with Pt electrodes are studied. The improved fatigue resistance of PZT and PLT at a low temperature can be explained by the defect-induced suppression of domain switch/nucleation near the film/electrode interface, which requires a long-range diffusion of defects and charges. It is argued that the fatigue effect of SBT and BLT is attributed to the competition between domain-wall pinning and depinning. The perovskitelike slabs and/or (Bi2O2)2+ layers act as barriers for long-range diffusion of defects and charges, resulting in localization of the defects and charges. Thus, the fatigued SBT and BLT can be easily rejuvenated by a high electric field over a wide temperature range.

  5. Oxidative Stress Increases the Blood Brain Barrier Permeability Resulting in Increased Incidence of Brain Metastasis in BRCA Mutation Carriers

    DTIC Science & Technology

    2012-02-01

    inhibitors and/or selenium in preventing BBB-induced damage by oxidative stress, and in inhibiting breast cancer metastasis to the brain. Further...since selenium has anti- cancer properties that are linked with protection against oxidative stress and Poly (ADP-ribose) polymerase (PARP) inhibitors...BRCA1 in breast cancer cells resulted in an increase in cell proliferation, anchorage-independent growth, cell migration, invasion and a loss of p21

  6. Implication of oxidative stress in size-dependent toxicity of silica nanoparticles in kidney cells.

    PubMed

    Passagne, Isabelle; Morille, Marie; Rousset, Marine; Pujalté, Igor; L'azou, Béatrice

    2012-09-28

    Silica nanoparticles (nano-SiO(2)) are one of the most popular nanomaterials used in industrial manufacturing, synthesis, engineering and medicine. While inhalation of nanoparticles causes pulmonary damage, nano-SiO(2) can be transported into the blood and deposit in target organs where they exert potential toxic effects. Kidney is considered as such a secondary target organ. However, toxicological information of their effect on renal cells and the mechanisms involved remain sparse. In the present study, the cytotoxicity of nano-SiO(2) of different sizes was investigated on two renal proximal tubular cell lines (human HK-2 and porcine LLC-PK(1)). The molecular pathways involved were studied with a focus on the involvement of oxidative stress. Nanoparticle characterization was performed (primary nanoparticle size, surface area, dispersion) in order to investigate a potential relationship between their physical properties and their toxic effects. Firstly, evidence of particle internalization was obtained by transmission electron microscopy and conventional flux cytometry techniques. The use of specific inhibitors of endocytosis pathways showed an internalization process by macropinocytosis and clathrin-mediated endocytosis for 100 nm nano-SiO(2) nanoparticles. These nanoparticles were localized in vesicles. Toxicity was size- and time-dependent (24h, 48 h, 72 h). Indeed, it increased as nanoparticles became smaller. Secondly, analysis of oxidative stress based on the assessment of ROS (reactive oxygen species) production (DHE, dihydroethidium) or lipid peroxidation (MDA, malondialdehyde) clearly demonstrated the involvement of oxidative stress in the toxicity of 20 nm nano-SiO(2). The induction of antioxidant enzymes (catalase, GSTpi, thioredoxin reductase) could explain their lesser toxicity with 100 nm nano-SiO(2).

  7. CD36 binds oxidized low density lipoprotein (LDL) in a mechanism dependent upon fatty acid binding.

    PubMed

    Jay, Anthony G; Chen, Alexander N; Paz, Miguel A; Hung, Justin P; Hamilton, James A

    2015-02-20

    The association of unesterified fatty acid (FA) with the scavenger receptor CD36 has been actively researched, with focuses on FA and oxidized low density lipoprotein (oxLDL) uptake. CD36 has been shown to bind FA, but this interaction has been poorly characterized to date. To gain new insights into the physiological relevance of binding of FA to CD36, we characterized FA binding to the ectodomain of CD36 by the biophysical method surface plasmon resonance. Five structurally distinct FAs (saturated, monounsaturated (cis and trans), polyunsaturated, and oxidized) were pulsed across surface plasmon resonance channels, generating association and dissociation binding curves. Except for the oxidized FA HODE, all FAs bound to CD36, with rapid association and dissociation kinetics similar to HSA. Next, to elucidate the role that each FA might play in CD36-mediated oxLDL uptake, we used a fluorescent oxLDL (Dii-oxLDL) live cell assay with confocal microscopy imaging. CD36-mediated uptake in serum-free medium was very low but greatly increased when serum was present. The addition of exogenous FA in serum-free medium increased oxLDL binding and uptake to levels found with serum and affected CD36 plasma membrane distribution. Binding/uptake of oxLDL was dependent upon the FA dose, except for docosahexaenoic acid, which exhibited binding to CD36 but did not activate the uptake of oxLDL. HODE also did not affect oxLDL uptake. High affinity FA binding to CD36 and the effects of each FA on oxLDL uptake have important implications for protein conformation, binding of other ligands, functional properties of CD36, and high plasma FA levels in obesity and type 2 diabetes.

  8. Roles of thioredoxin in nitric oxide-dependent preconditioning-induced tolerance against MPTP neurotoxin

    SciTech Connect

    Chiueh, C.C. . E-mail: chiueh@tmu.edu.tw; Andoh, Tsugunobu; Chock, P. Boon

    2005-09-01

    Hormesis, a stress tolerance, can be induced by ischemic preconditioning stress. In addition to preconditioning, it may be induced by other means, such as gas anesthetics. Preconditioning mechanisms, which may be mediated by reprogramming survival genes and proteins, are obscure. A known neurotoxicant, 1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), causes less neurotoxicity in the mice that are preconditioned. Pharmacological evidences suggest that the signaling pathway of {center_dot}NO-cGMP-PKG (protein kinase G) may mediate preconditioning phenomenon. We developed a human SH-SY5Y cell model for investigating {sup {center_dot}}NO-mediated signaling pathway, gene regulation, and protein expression following a sublethal preconditioning stress caused by a brief 2-h serum deprivation. Preconditioned human SH-SY5Y cells are more resistant against severe oxidative stress and apoptosis caused by lethal serum deprivation and 1-mehtyl-4-phenylpyridinium (MPP{sup +}). Both sublethal and lethal oxidative stress caused by serum withdrawal increased neuronal nitric oxide synthase (nNOS/NOS1) expression and {sup {center_dot}}NO levels to a similar extent. In addition to free radical scavengers, inhibition of nNOS, guanylyl cyclase, and PKG blocks hormesis induced by preconditioning. S-nitrosothiols and 6-Br-cGMP produce a cytoprotection mimicking the action of preconditioning tolerance. There are two distinct cGMP-mediated survival pathways: (i) the up-regulation of a redox protein thioredoxin (Trx) for elevating mitochondrial levels of antioxidant protein Mn superoxide dismutase (MnSOD) and antiapoptotic protein Bcl-2, and (ii) the activation of mitochondrial ATP-sensitive potassium channels [K(ATP)]. Preconditioning induction of Trx increased tolerance against MPP{sup +}, which was blocked by Trx mRNA antisense oligonucleotide and Trx reductase inhibitor. It is concluded that Trx plays a pivotal role in {sup {center_dot}}NO-dependent preconditioning hormesis against

  9. Differential oxidative modulation of voltage-dependent K+ currents in rat hippocampal neurons.

    PubMed

    Müller, Wolfgang; Bittner, Katrin

    2002-06-01

    Oxidative stress is enhanced by [Ca2+]i-dependent stimulation of phospholipases and mitochondria and has been implicated in immune defense, ischemia, and excitotoxicity. Using whole cell recording from hippocampal neurons, we show that arachidonic acid (AA) and hydrogen peroxide (H2O2) both reduce the transient K+ current I(A) by -54 and -68%, respectively, and shift steady-state inactivation by -10 and -15 mV, respectively. While AA was effective at an extracellular concentration of 1 microM and an intracellular concentration of 1 pM, extracellular H2O2 was equally effective only at a concentration >800 microM (0.0027%). In contrast to AA, H2O2 decreased the slope of activation and increased the slope of inactivation of I(A) and reduced the sustained delayed rectifier current I(K(V)) by 22% and shifted its activation by -9 mV. Intracellular application of the antioxidant glutathione (GSH, 2-5 mM) blocked all effects of AA and the reduction of I(A) by H2O2. In contrast, intracellular GSH enhanced reduction of I(K(V)) by H2O2. Decrease of the slope of activation and increase of the slope of inactivation of I(A) by hydrogen peroxide was blocked and reversed to a decrease, respectively, by intracellular application of GSH. Intracellular GSH did not prevent H2O2 to shift inactivation and activation of I(A) and activation of I(K(V)) to more negative potentials. We conclude, that AA and H2O2 modulate voltage-activated K currents differentially by oxidation of GSH accessible intracellular and GSH inaccessible extracellular K+-channel domains, thereby presumably affecting neuronal information processing and oxidative damage.

  10. Oxidative stress-dependent conversion of hydrogen sulfide to sulfite by activated neutrophils.

    PubMed

    Mitsuhashi, Hideki; Yamashita, Shin; Ikeuchi, Hidekazu; Kuroiwa, Takashi; Kaneko, Yoriaki; Hiromura, Keiju; Ueki, Kazue; Nojima, Yoshihisa

    2005-12-01

    Sulfite, which is known as a major constituent of volcanic gas, is endogenously produced in mammals, and its concentration in serum is increased in patients with pneumonia. It has been reported that sulfite is produced by oxidation from hydrogen sulfide (H2S) as an intermediate in the mammalian body. The objective of this study was to investigate the ability of reactive oxygen species from neutrophils to produce sulfite from H2S. Sulfite production from activated neutrophils stimulated with N-formyl-methionyl-leucyl-phenylalanine gradually increased with an increased concentration of sodium hydrosulfide (NaHS) in the medium. The production of sulfite was markedly suppressed with an NADPH oxidase inhibitor, diphenyleneiodonium. When NaHS was added to the supernatant of activated neutrophils, a significant amount of sulfite was synthesized in the test tubes. Furthermore, when a medium containing NaHS was incubated with a water-soluble radical initiator, 2,2'-azobis-(amidinopropane) dihydrochloride, sulfite was formed in the solution and this increase was markedly suppressed by ascorbic acid. Finally, we determined serum concentrations of sulfite and H2S in an in vivo model of neutrophil activation induced by systemic injection of lipopolysaccharide (LPS) into rats. We found a significant increase in serum sulfite and H2S after LPS injection. Importantly, coadministration of ascorbic acid with LPS further increased serum H2S but suppressed sulfite levels. This finding implies that oxidative stress-dependent conversion of H2S to sulfite might occur in vivo. Thus, the oxidation of H2S is a novel sulfite production pathway in the inflammatory condition, and this chemical synthesis might be responsible for the upregulation of sulfite production in inflammatory conditions such as pneumonia.

  11. PTR1-dependent synthesis of tetrahydrobiopterin contributes to oxidant susceptibility in the trypanosomatid protozoan parasite Leishmania major

    PubMed Central

    Nare, Bakela; Garraway, Levi A.; Vickers, Tim J.; Beverley, Stephen M.

    2009-01-01

    Leishmania must survive oxidative stress, but lack many classical antioxidant enzymes and rely heavily on trypanothione-dependent pathways. We used forward genetic screens to recover loci mediating oxidant resistance via overexpression in Leishmania major, which identified pteridine reductase 1 (PTR1). Comparisons of isogenic lines showed ptr1- null mutants were 18-fold more sensitive to H2O2 than PTR1-overproducing lines, and significant 3-5 fold differences were seen with a broad panel of oxidant-inducing agents. The toxicities of simple nitric oxide generators and other drug classes (except antifolates) were unaffected by PTR1 levels. H2O2 susceptibility could be modulated by exogenous biopterin but not folate, in a PTR1-but not dihydrofolate reductase-dependent manner, implicating H4B metabolism specifically. Neither H2O2 consumption, nor the level of intracellular oxidative stress, was affected by PTR1 levels. Coupled with the fact that reduced pteridines are at least 100-fold less abundant than cellular thiols), these data argue strongly that reduced pteridines act through a mechanism other than scavenging. The ability of unconjugated pteridines to counter oxidative stress has implications to infectivity and response to chemotherapy. Since the intracellular pteridine levels of Leishmania can be readily manipulated, these organisms offer a powerful setting for the dissection of pteridine-dependent oxidant susceptibility in higher eukaryotes. PMID:19396443

  12. Chemical and structural investigation of the role of both Mn and Mn oxide in the formation of manganese silicate barrier layers on SiO{sub 2}

    SciTech Connect

    Casey, P.; Bogan, J.; Hughes, G.; Lozano, J. G.; Nellist, P. D.

    2011-09-01

    In this study, Mn silicate (MnSiO{sub 3}) barrier layers were formed on thermally grown SiO{sub 2} using both metallic Mn and oxidized Mn films, in order to investigate the role of oxygen in determining the extent of the interaction between the deposited Mn and the SiO{sub 2} substrate. Using x-ray photoelectron spectroscopy, it has been shown that a metallic Mn film with an approximate thickness of 1 nm cannot be fully converted to Mn silicate following vacuum annealing to 500 deg. C. Transmission electron microscopy (TEM) analysis suggests the maximum MnSiO{sub 3} layer thickness obtainable using metallic Mn is {approx}1.7 nm. In contrast, a {approx}1 nm partially oxidized Mn film can be fully converted to Mn silicate following thermal annealing to 400 deg. C, forming a MnSiO{sub 3} layer with a measured thickness of 2.6 nm. TEM analysis also clearly shows that MnSiO{sub 3} growth results in a corresponding reduction in the SiO{sub 2} layer thickness. It has also been shown that a fully oxidized Mn oxide thin film can be converted to Mn silicate, in the absence of metallic Mn. Based on these results it is suggested that the presence of Mn oxide species at the Mn/SiO{sub 2} interface facilitates the conversion of SiO{sub 2} to MnSiO{sub 3}, in agreement with previously published studies.

  13. Time and voltage dependences of nanoscale dielectric constant modulation on indium tin oxide films

    NASA Astrophysics Data System (ADS)

    Li, Liang; Hao, Haoyue; Zhao, Hua

    2017-01-01

    The modulation of indium tin oxide (ITO) films through surface charge accumulation plays an important role in many different applications. In order to elaborately study the modulation, we measured the dielectric constant of the modulated layer through examining the excitation of surface plasmon polaritons. Charges were pumped on the surfaces of ITO films through applying high voltage in appropriate directions. Experiments unveiled that the dielectric constant of the modulated layer had large variation along with the nanoscale charge accumulation. Corresponding numerical results were worked out through combining Drude model and Mayadas-Shatzkes model. Based on the above results, we deduced the time and voltage dependences of accumulated charge density, which revealed a long-time charge accumulation process.

  14. [Nitrate removal by a strain of nitrate-dependent Fe (II) -oxidizing bacteria].

    PubMed

    Wang, Hong-Yu; Yang, Kai; Zhang, Qian; Ji, Bin; Chen, Dan; Sun, Yu-Chong; Tian, Jun

    2014-04-01

    A nitrate-dependent Fe(II)-oxidizing bacterial strain, named W5, was isolated from the sediment of the East Lake in Wuhan. Strain W5 was studied for its characteristics of denitrification and nitrogen removal. According to its physiological and biochemical characteristics and the analysis of its 16S rRNA gene sequence, strain W5 was identified as Microbacterium sp. The optimal denitrification performance can be obtained under conditions of NO3(-) -N 40 mg x L(-1), Fe2+ 500 mg x L(-1) and pH 6.8-7.0. After one week of cultivation under optimal conditions, nitrate removal percentage reached 87.0%. During the process of the culture, the nitrite nitrogen concentration was no more than 0.31 mg x L(-1) and there was no ammonia nitrogen production. It was indicated that the nitrate was mostly converted into N2. The consumption rate of Fe2+ was 95.2%.

  15. Thickness dependence of mechanical properties of free-standing graphene oxide papers

    NASA Astrophysics Data System (ADS)

    Gong, Tao; Lam, Do Van; Won, Sejeong; Liu, Renlong; Yun, Hwangbo; Kwon, Sanghyuk; Kim, Jinseon; Sun, Ke; Lee, Seungmo; Lee, Changgu; Graphene engineering lab Team; Nanomechanics Lab Collaboration

    2015-03-01

    We have characterized thickness dependence of mechanical properties, such as Young's modulus, fracture strength, fracture strain and toughness, of graphene oxide papers using tensile and bulge test methods. The GO papers were made from Hummer's method and the fabricated GO paper's thickness varied from 0.1 ~ 100 μm. The measured Young's modulus and fracture strength decreased with increasing thickness ranging from 44.6 ~ 8.5GPa and 170.2 ~ 40MPa respectively. Through TEM, SEM and AFM characterization, the inner structure and surface morphology such as crack formation and roughness change are the keys to the variation of mechanical properties in the GO papers by the thickness. The thicker GO papers are weaker because it has more manufacturing voids in it that cause it to fail easily and less stiff. Surface wrinkle and residual stress are the mechanism of terraced fracture strain.

  16. Size dependent biodistribution and toxicokinetics of iron oxide magnetic nanoparticles in mice

    NASA Astrophysics Data System (ADS)

    Yang, Lin; Kuang, Huijuan; Zhang, Wanyi; Aguilar, Zoraida P.; Xiong, Yonghua; Lai, Weihua; Xu, Hengyi; Wei, Hua

    2014-12-01

    In spite of the immense benefits from iron oxide magnetic nanoparticles (IOMNs), there is scanty information regarding their metabolic activities and toxicity in vivo. In this study, we investigated the size dependent in vivo biodistribution, toxicokinetics, and toxicity and gene expression changes of various sizes of carboxyl coated IOMNs (diameters of 10, 20, 30, and 40 nm). Our findings demonstrated that the various sizes of IOMNs accumulated primarily in the liver and spleen on the first day post-injection. Interestingly, size dependent biodistribution and transport were observed: the smallest IOMNs (10 nm) showed the highest uptake by the liver, whereas the largest IOMNs (40 nm) showed the highest uptake by the spleen. Moreover, the IOMNs with the smallest size (10 nm) were cleared faster from the liver and kidneys, but more readily entered the brain and the uterus. IOMNs with the largest size (40 nm) accumulated more readily but were easily eliminated in the spleen. However, the level of iron in the heart decreased in all IOMN exposed groups. In addition, blood biochemistry, hematological analyses and histological examination demonstrated that there was no apparent acute toxicity caused by IOMNs in mice. However, smaller IOMNs (10 nm and 20 nm) more effectively changed the expression level of sensitive genes related to oxidant stress, iron transport, metabolic process, apoptosis, and others.In spite of the immense benefits from iron oxide magnetic nanoparticles (IOMNs), there is scanty information regarding their metabolic activities and toxicity in vivo. In this study, we investigated the size dependent in vivo biodistribution, toxicokinetics, and toxicity and gene expression changes of various sizes of carboxyl coated IOMNs (diameters of 10, 20, 30, and 40 nm). Our findings demonstrated that the various sizes of IOMNs accumulated primarily in the liver and spleen on the first day post-injection. Interestingly, size dependent biodistribution and transport

  17. Spleen Tyrosine Kinase Regulates AP-1 Dependent Transcriptional Response to Minimally Oxidized LDL

    PubMed Central

    Choi, Soo-Ho; Wiesner, Philipp; Almazan, Felicidad; Kim, Jungsu; Miller, Yury I.

    2012-01-01

    Oxidative modification of low-density lipoprotein (LDL) turns it into an endogenous ligand recognized by pattern-recognition receptors. We have demonstrated that minimally oxidized LDL (mmLDL) binds to CD14 and mediates TLR4/MD-2-dependent responses in macrophages, many of which are MyD88-independent. We have also demonstrated that the mmLDL activation leads to recruitment of spleen tyrosine kinase (Syk) to TLR4 and TLR4 and Syk phosphorylation. In this study, we produced a macrophage-specific Syk knockout mouse and used primary Syk−/− macrophages in our studies. We demonstrated that Syk mediated phosphorylation of ERK1/2 and JNK, which in turn phosphorylated c-Fos and c-Jun, respectively, as assessed by an in vitro kinase assay. c-Jun phosphorylation was also mediated by IKKε. c-Jun and c-Fos bound to consensus DNA sites and thereby completed an AP-1 transcriptional complex and induced expression of CXCL2 and IL-6. These results suggest that Syk plays a key role in TLR4-mediated macrophage responses to host-generated ligands, like mmLDL, with subsequent activation of an AP-1 transcription program. PMID:22384232

  18. Copper control of bacterial nitrous oxide emission and its impact on vitamin B12-dependent metabolism.

    PubMed

    Sullivan, Matthew J; Gates, Andrew J; Appia-Ayme, Corinne; Rowley, Gary; Richardson, David J

    2013-12-03

    Global agricultural emissions of the greenhouse gas nitrous oxide (N2O) have increased by around 20% over the last 100 y, but regulation of these emissions and their impact on bacterial cellular metabolism are poorly understood. Denitrifying bacteria convert nitrate in soils to inert di-nitrogen gas (N2) via N2O and the biochemistry of this process has been studied extensively in Paracoccus denitrificans. Here we demonstrate that expression of the gene encoding the nitrous oxide reductase (NosZ), which converts N2O to N2, is regulated in response to the extracellular copper concentration. We show that elevated levels of N2O released as a consequence of decreased cellular NosZ activity lead to the bacterium switching from vitamin B12-dependent to vitamin B12-independent biosynthetic pathways, through the transcriptional modulation of genes controlled by vitamin B12 riboswitches. This inhibitory effect of N2O can be rescued by addition of exogenous vitamin B12.

  19. Photo-isomerization and oxidation of bilirubin in mammals is dependent on albumin binding.

    PubMed

    Goncharova, Iryna; Jašprová, Jana; Vítek, Libor; Urbanová, Marie

    2015-12-01

    The bilirubin (BR) photo-conversion in the human body is a protein-dependent process; an effective photo-isomerization of the potentially neurotoxic Z,Z-BR as well as its oxidation to biliverdin in the antioxidant redox cycle is possible only when BR is bound on serum albumin. We present a novel analytical concept in the study of linear tetrapyrroles metabolic processes based on an in-depth mapping of binding sites in the structure of human serum albumin (HSA). A combination of fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and molecular modeling methods was used for recognition of the binding site for BR, its derivatives (mesobilirubin and bilirubin ditaurate), and the products of the photo-isomerization and oxidation (lumirubin, biliverdin, and xanthobilirubic acid) on HSA. The CD spectra and fluorescent quenching of the Trp-HSA were used to calculate the binding constants. The results of the CD displacement experiments performed with hemin were interpreted together with the findings of molecular docking performed on the pigment-HSA complexes. We estimated that Z,Z-BR and its metabolic products bind on two independent binding sites. Our findings support the existence of a reversible antioxidant redox cycle for BR and explain an additional pathway of the photo-isomerization process (increase of HSA binding capacity; the excess free [unbound] BR can be converted and also bound to HSA).

  20. Nitric Oxide Mediates the Glutamate-dependent Pathway for Neurotransmission in Sepia officinalis Chromatophore Organs

    PubMed Central

    Mattiello, Teresa; Fiore, Gabriella; Brown, Euan R.; d'Ischia, Marco; Palumbo, Anna

    2010-01-01

    Chromatophore organs are complex and unique structures responsible for the variety of body coloration patterns used by cephalopods to communicate and camouflage. They are formed by a pigment-containing cytoelastic sacculus, surrounded by muscle fibers directly innervated from the brain. Muscle contraction and relaxation are responsible for expansion and retraction of the pigment-containing cell. Their functioning depends on glutamate and Phe-Met-Arg-Phe-NH2-related peptides, which induce fast and slow cell expansion, respectively, and 5-hydroxytryptamine, which induces retraction. Apart from these three substances and acetylcholine, which acts presynaptically, no other neuroactive compounds have so far been found to be involved in the neuroregulation of chromatophore physiology, and the detailed signaling mechanisms are still little understood. Herein, we disclose the role of nitric oxide (NO) as mediator in one of the signaling pathways by which glutamate activates body patterning. NO and nitric-oxide synthase have been detected in pigment and muscle fibers of embryo, juvenile, and adult chromatophore organs from Sepia officinalis. NO-mediated Sepia chromatophore expansion operates at slower rate than glutamate and involves cGMP, cyclic ADP-ribose, and ryanodine receptor activation. These results demonstrate for the first time that NO is an important messenger in the long term maintenance of the body coloration patterns in Sepia. PMID:20516065

  1. Mdodeling a nitrite-dependent anaerobic methane oxidation process: parameters identification and model evaluation.

    PubMed

    He, Zhanfei; Cai, Chen; Geng, Sha; Lou, Liping; Xu, Xiangyang; Zheng, Ping; Hu, Baolan

    2013-11-01

    Nitrite-dependent anaerobic methane oxidation (n-damo) is a recently discovered process that is intermediated by n-damo bacteria that oxidize methane with nitrite to generate nitrogen gas. In this work, a kinetic model based on Monod type kinetics and diffusion-reaction model was developed to describe the bioprocess. Some key kinetic parameters needed in the model were obtained from a series of batch activity tests and a sequencing batch reactor (SBR) operation over 100 days. The growth rate, decay rate, methane affinity constant, nitrite affinity constant and inhibition constant were 0.0277±0.0022 d(-1), 0.00216±0.00010 d(-1), 0.092±0.005 mmol L(-1), 0.91±0.09 mmol L(-1) and 4.1±0.5 mmol L(-1) for n-damo bacteria at 30 °C, respectively. The results showed that the model could simulate actual performance of the SBR in the first 76 days, that methane was not a limiting factor at atmospheric pressure for its high affinity, and that the optimum nitrite concentration was 1.92 mmol L(-1).

  2. Denitrification and Nitrate-Dependent Fe(II) Oxidation in Various Pseudogulbenkiania Strains

    PubMed Central

    Ishii, Satoshi; Joikai, Kazuki; Otsuka, Shigeto; Senoo, Keishi; Okabe, Satoshi

    2016-01-01

    Pseudogulbenkiania is a relatively recently characterized genus within the order Neisseriales, class Betaproteobacteria. This genus contains several strains that are capable of anaerobic, nitrate-dependent Fe(II) oxidation (NDFO), a geochemically important reaction for nitrogen and iron cycles. In the present study, we examined denitrification functional gene diversities within this genus, and clarified whether other Pseudogulbenkiania sp. strains perform denitrification and NDFO. Seventy strains were analyzed, including two type strains, a well-characterized NDFO strain, and 67 denitrifying strains isolated from various rice paddy fields and rice-soybean rotation fields in Japan. We also attempted to identify the genes responsible for NDFO by mutagenesis. Our comprehensive analysis showed that all Pseudogulbenkiania strains tested performed denitrification and NDFO; however, we were unable to obtain NDFO-deficient denitrifying mutants in our mutagenesis experiment. This result suggests that Fe(II) oxidation in these strains is not enzymatic, but is caused by reactive N-species that are formed during nitrate reduction. Based on the results of the comparative genome analysis among Pseudogulbenkiania sp. strains, we identified low sequence similarity within the nos gene as well as different gene arrangements within the nos gene cluster, suggesting that nos genes were horizontally transferred. Since Pseudogulbenkiania sp. strains have been isolated from various locations around the world, their denitrification and NDFO abilities may contribute significantly to nitrogen and iron biogeochemical cycles. PMID:27431373

  3. The Iron-Dependent Regulation of the Candida albicans Oxidative Stress Response by the CCAAT-Binding Factor

    PubMed Central

    Chakravarti, Ananya; Camp, Kyle; McNabb, David S.

    2017-01-01

    Candida albicans is the most frequently encountered fungal pathogen in humans, capable of causing mucocutaneous and systemic infections in immunocompromised individuals. C. albicans virulence is influenced by multiple factors. Importantly, iron acquisition and avoidance of the immune oxidative burst are two critical barriers for survival in the host. Prior studies using whole genome microarray expression data indicated that the CCAAT-binding factor is involved in the regulation of iron uptake/utilization and the oxidative stress response. This study examines directly the role of the CCAAT-binding factor in regulating the expression of oxidative stress genes in response to iron availability. The CCAAT-binding factor is a heterooligomeric transcription factor previously shown to regulate genes involved in respiration and iron uptake/utilization in C. albicans. Since these pathways directly influence the level of free radicals, it seemed plausible the CCAAT-binding factor regulates genes necessary for the oxidative stress response. In this study, we show the CCAAT-binding factor is involved in regulating some oxidative stress genes in response to iron availability, including CAT1, SOD4, GRX5, and TRX1. We also show that CAT1 expression and catalase activity correlate with the survival of C. albicans to oxidative stress, providing a connection between iron obtainability and the oxidative stress response. We further explore the role of the various CCAAT-binding factor subunits in the formation of distinct protein complexes that modulate the transcription of CAT1 in response to iron. We find that Hap31 and Hap32 can compensate for each other in the formation of an active transcriptional complex; however, they play distinct roles in the oxidative stress response during iron limitation. Moreover, Hap43 was found to be solely responsible for the repression observed under iron deprivation. PMID:28122000

  4. Cellular Metabolism and Dose Reveal Carnitine-Dependent and -Independent Mechanisms of Butyrate Oxidation in Colorectal Cancer Cells.

    PubMed

    Han, Anna; Bennett, Natalie; MacDonald, Amber; Johnstone, Megan; Whelan, Jay; Donohoe, Dallas R

    2016-08-01

    Dietary fiber has been suggested to suppress colorectal cancer development, although the mechanisms contributing to this beneficial effect remain elusive. Butyrate, a fermentation product of fiber, has been shown to have anti-proliferative and pro-apoptotic effects on colorectal cancer cells. The metabolic fate of butyrate in the cell is important in determining whether, it acts as an HDAC inhibitor or is consumed as a short-chain fatty acid. Non-cancerous colonocytes utilize butyrate as the primary energy source whereas cancerous colonocytes increase glucose utilization through the Warburg effect. In this study, we show that butyrate oxidation is decreased in cancerous colonocytes compared to non-cancerous colonocytes. We demonstrate that colorectal cancer cells utilize both a carnitine-dependent and carnitine-independent mechanism that contributes to butyrate oxidation. The carnitine-dependent mechanism is contingent on butyrate concentration. Knockdown of CPT1A in colorectal cancer cells abolishes butyrate oxidation. In terms of selectivity, the carnitine-dependent mechanism only regulated butyrate oxidation, as acetate and propionate oxidation were carnitine-independent. Carnitine decreased the action of butyrate as an HDAC inhibitor and suppressed induction of H3 acetylation by butyrate in colorectal cancer cells. Thus, diminished oxidation of butyrate is associated with decreased HDAC inhibition and histone acetylation. In relation to the mechanism, we find that dichloroacetate, which decreases phosphorylation of pyruvate dehydrogenase, increased butyrate oxidation and that this effect was carnitine-dependent. In conclusion, these data suggest that colorectal cancer cells decrease butyrate oxidation through inhibition of pyruvate dehydrogenase, which is carnitine-dependent, and provide insight into why butyrate shows selective effects toward colorectal cancer cells. J. Cell. Physiol. 231: 1804-1813, 2016. © 2015 Wiley Periodicals, Inc.

  5. Energy dependence of the optical potentials for the 9Be +208Pb and 9Be +209Bi systems at near-Coulomb-barrier energies

    NASA Astrophysics Data System (ADS)

    Gómez Camacho, A.; Yu, N.; Zhang, H. Q.; Gomes, P. R. S.; Jia, H. M.; Lubian, J.; Lin, C. J.

    2015-04-01

    We analyze the energy dependence of the interacting optical potential, at near barrier energies, for two systems involving the weakly bound projectile 9Be and the heavy 208Pb and 209Bi targets, by the simultaneous fit of elastic scattering angular distributions and fusion excitation functions. The approach used consists of dividing the optical potential into two parts. A short-range potential VF+i WF that is responsible for fusion, and a superficial potential VDR+i WDR for direct reactions. It is found, for both systems studied, that the fusion imaginary potential WF presents the usual threshold anomaly (TA) observed in tightly bound systems, whereas the direct reaction imaginary potential WDR shows a breakup threshold anomaly (BTA) behavior. Both potentials satisfy the dispersion relation. The direct reaction polarization potential predominates over the fusion potential and so a net overall behavior is found to follow the BTA phenomenon.

  6. Chemoprevention of oxidative stress-associated oral carcinogenesis by sulforaphane depends on NRF2 and the isothiocyanate moiety.

    PubMed

    Lan, Aixian; Li, Wenjun; Liu, Yao; Xiong, Zhaohui; Zhang, Xinyan; Zhou, Shanshan; Palko, Olesya; Chen, Hao; Kapita, Mayanga; Prigge, Justin R; Schmidt, Edward E; Chen, Xin; Sun, Zheng; Chen, Xiaoxin Luke

    2016-08-16

    Oxidative stress is known to play an important role in oral cancer development. In this study we aimed to examine whether a chemical activator of NRF2, sulforaphane (SFN), may have chemopreventive effects on oxidative stress-associated oral carcinogenesis. We first showed that Nrf2 activation and oxidative damage were commonly seen in human samples of oral leukoplakia. With gene microarray and immunostaining, we found 4-nitroquinoline 1-oxide (4NQO) in drink activated the Nrf2 pathway and produced oxidative damage in mouse tongue. Meanwhile whole exome sequencing of mouse tongue identified mutations consistent with 4NQO's mutagenic profile. Using cultured human oral keratinocytes and 4NQO-treated mouse tongue, we found that SFN pre-treatment activated the NRF2 pathway and inhibited oxidative damage both in vitro and in vivo. On the contrary, a structural analogue of SFN without the isothiocyanate moiety did not have such effects. In a long-term chemoprevention study using wild-type and Nrf2-/- mice, we showed that topical application of SFN activated the NRF2 pathway, inhibited oxidative damage, and prevented 4NQO-induced oral carcinogenesis in an Nrf2-dependent manner. Our data clearly demonstrate that SFN has chemopreventive effects on oxidative stress-associated oral carcinogenesis, and such effects depend on Nrf2 and the isothiocyanate moiety.

  7. Chemoprevention of oxidative stress-associated oral carcinogenesis by sulforaphane depends on NRF2 and the isothiocyanate moiety

    PubMed Central

    Liu, Yao; Xiong, Zhaohui; Zhang, Xinyan; Zhou, Shanshan; Palko, Olesya; Chen, Hao; Kapita, Mayanga; Prigge, Justin R.; Schmidt, Edward E.; Chen, Xin; Sun, Zheng; Chen, Xiaoxin Luke

    2016-01-01

    Oxidative stress is known to play an important role in oral cancer development. In this study we aimed to examine whether a chemical activator of NRF2, sulforaphane (SFN), may have chemopreventive effects on oxidative stress-associated oral carcinogenesis. We first showed that Nrf2 activation and oxidative damage were commonly seen in human samples of oral leukoplakia. With gene microarray and immunostaining, we found 4-nitroquinoline 1-oxide (4NQO) in drink activated the Nrf2 pathway and produced oxidative damage in mouse tongue. Meanwhile whole exome sequencing of mouse tongue identified mutations consistent with 4NQO's mutagenic profile. Using cultured human oral keratinocytes and 4NQO-treated mouse tongue, we found that SFN pre-treatment activated the NRF2 pathway and inhibited oxidative damage both in vitro and in vivo. On the contrary, a structural analogue of SFN without the isothiocyanate moiety did not have such effects. In a long-term chemoprevention study using wild-type and Nrf2-/- mice, we showed that topical application of SFN activated the NRF2 pathway, inhibited oxidative damage, and prevented 4NQO-induced oral carcinogenesis in an Nrf2-dependent manner. Our data clearly demonstrate that SFN has chemopreventive effects on oxidative stress-associated oral carcinogenesis, and such effects depend on Nrf2 and the isothiocyanate moiety. PMID:27447968

  8. Nitric oxide triggers specific and dose-dependent cytosolic calcium transients in Arabidopsis.

    PubMed

    Aboul-Soud, Mourad A M; Aboul-Enein, Ahmed M; Loake, Gary J

    2009-03-01

    Calcium (Ca(2+)) transients have been shown to take place in response to diverse developmental and physiological cues. Also, it is involved in biotic and abiotic stress signaling. Nitric oxide (NO) is an important signaling molecule that plays a crucial role in plant growth and development, starting from germination to flowering, ripening of fruit and senescence of organs. Moreover, it plays a pivotal role in several biotic and abiotic stress signaling processes. In the present work, the ability of NO to trigger increases in cytosolic calcium concentration ([Ca(2+)](cyt)) was investigated. For this purpose, transgenic Arabidopsis seedlings constitutively expressing the luminescent Ca(2+)-sensitive protein apoaequorin (35S::APOAEQUORIN) was employed. In chemiluminescence and in vivo Ca(2+) imaging assays, the NO-donor sodium nitroprusside (SNP) triggered a strong, instantaneous, reproducible, and dose-dependent rise in [Ca(2+)](cyt). Moreover, the observed rise in [Ca(2+)](cyt) was shown to be NO-specific and not associated with decomposition products of SNP, as the NO-scavenger 2-4-carboxyphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3 oxide (C-PTIO) significantly blunted the observed NO-mediated spike in [Ca(2+)](cyt). Interestingly, preincubation of 35S::APOAEQUORIN Arabidopsis seedlings with the plasma membrane channel blocker lanthanum chloride resulted in partial concentration-dependent blocking of the NO-specific Ca(2+) transient. This observation indicates that, in addition to the mobilization of [Ca(2+)](cyt), as an external source in response to NO treatment, there also exists an appreciable contribution of an as yet unidentified internal pool.

  9. Oxidation of methionine in PrP is dependent upon the oxidant and the amino acid two positions removed

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Background/Introduction. Methionine oxidation has been shown both to be associated with prion formation and implicated in the inhibition of amyloid formation in model systems. This work is based on model systems where hydrogen peroxide was used as an oxidant. Materials and Methods. We developed...

  10. Acute dairy milk ingestion does not improve nitric oxide-dependent vasodilation in the cutaneous microcirculation.

    PubMed

    Alba, Billie K; Stanhewicz, Anna E; Kenney, W Larry; Alexander, Lacy M

    2016-07-01

    In epidemiological studies, chronic dairy milk consumption is associated with improved vascular health and reduced age-related increases in blood pressure. Although milk protein supplementation augments conduit artery flow-mediated dilation, whether or not acute dairy milk intake may improve microvascular function remains unclear. We hypothesised that dairy milk would increase direct measurement of endothelial nitric oxide (NO)-dependent cutaneous vasodilation in response to local skin heating. Eleven men and women (61 (sem 2) years) ingested two or four servings (473 and 946 ml) of 1 % dairy milk or a rice beverage on each of 4 separate study days. In a subset of five subjects, an additional protocol was completed after 473 ml of water ingestion. Once a stable blood flow occurred, 15 mm-N G -nitro-l-arginine methyl ester was perfused (intradermal microdialysis) to quantify NO-dependent vasodilation. Red-blood-cell flux (RBF) was measured by laser-Doppler flowmetry, and cutaneous vascular conductance (CVC=RBF/mean arterial pressure) was calculated and normalised to maximum (%CVCmax; 28 mm-sodium nitroprusside). Full expression of cutaneous vasodilation was not different among dairy milk, rice beverage and water, and there was no effect of serving size on the total vasodilatory response. Contrary to our hypothesis, NO-dependent vasodilation was lower for dairy milk than rice beverage (D: 49 (sem 5), R: 55 (sem 5) %CVCmax; P<0·01). Acute dairy milk ingestion does not augment NO-dependent vasodilation in the cutaneous microcirculation compared with a rice beverage control.

  11. Myocardial oxidative damage is induced by cardiac Fas-dependent and mitochondria-dependent apoptotic pathways in human cocaine-related overdose

    PubMed Central

    Turillazzi, Emanuela; Cerretani, Daniela; Cantatore, Santina; Fiaschi, Anna Ida; Frati, Paola; Micheli, Lucia; Neri, Margherita; Cipolloni, Luigi; Di Paolo, Marco; Pinchi, Enrica; Riezzo, Irene; Santurro, Alessandro; Vullo, Annamaria; Fineschi, Vittorio

    2017-01-01

    The aim of this study is to analyse cardiac specimens from human cocaine-related overdose, to verify the hypothesis that cardiac toxicity by acute exposure to high dosage of cocaine could be mediated by unbalanced myocardial oxidative stress, and to evaluate the apoptotic response. To address these issues, biochemical and immunohistological markers of oxidative/nitrosative stress were evaluated. We found that i-NOS, NOX2 and nitrotyrosine expression were significantly higher in the hearts of subjects who had died from high doses of cocaine, compared to the control group. Increase of these markers was associated with a dramatic increase in 8-OHdG, another marker of oxidative stress. A high number of TUNEL-positive apoptotic myocells was observed in the study group compared to the control group. The immunoexpression of TNF-α was significantly higher in the cocaine group compared to the control group. Furthermore, we detected a significantly stronger immunoresponse to anti-SMAC/DIABLO in our study group compared to control cases. Both cardiac Fas-dependent and mitochondria-dependent apoptotic pathways appeared to be activated to a greater extent in the cocaine group than in the control group. Our results highlight the central role of oxidative stress in cocaine toxicity. High levels of NOS can promote the oxidation process and lead to apoptosis. PMID:28281685

  12. Oxygen as Intermediate in Anoxic Environments: Nitrite-Dependent Methane Oxidation and Beyond

    NASA Astrophysics Data System (ADS)

    Ettwig, K. F.

    2014-12-01

    In recent years the known diversity of hydrocarbon activation mechanisms under anaerobic conditions has been extended by intra-aerobic denitrification, a process in which oxygen is derived from NO and used for substrate activation. For two phylogenetically unrelated bacterial species, the freshwater NC10 phylum bacterium Methylomirabilis oxyfera [1] and the marine γ-proteobacterial strain HdN1 [2] it has been shown that, under anoxic conditions with nitrate and/or nitrite, mono-oxygenases are used for methane and hexadecane oxidation, respectively. No degradation was observed with nitrous oxide (N2O) only. In the anaerobic methanotroph M. oxyfera, which lacks apparent nitrous oxide reductase in its genome, substrate activation in the presence of nitrite was directly associated with both O2 and N2 formation. These findings strongly argue for the role of nitric oxide (NO), or an oxygen species derived from it, in the activation reaction of methane. Although intracellular oxygen generation has been experimentally documented and elegantly explains the utilization of 'aerobic' pathways under anoxic conditions, research about the underlying molecular mechanism has just started. The proposed candidate enzymes for oxygen (or possibly another another reactive intermediate) production from NO, an NO dismutase (NOD) [3], related to quinol-dependent NO reductases (qNORs), is present and highly expressed in both M. oxyfera and strain HdN1. Besides that, several recently sequenced species from the Cytophaga-Flavobacterium-Bacteroides group harbor Nod/Nor genes, but experimential evidence is needed to show if these have NOD activity, are unusual but functional qNORs, or represent transition states between the two. Additionally, for several anaerobic hydrocarbon-degrading organisms the biochemical mechanism of substrate activation has not been elucidated yet: whereas signature genes of anaerobic degradation are missing, monooxygenase genes are present. Also these microorganisms

  13. Oxidation of tolualdehydes to toluic acids catalyzed by cytochrome P450-dependent aldehyde oxygenase in the mouse liver.

    PubMed

    Watanabe, K; Matsunaga, T; Yamamoto, I; Yashimura, H

    1995-02-01

    Mouse hepatic microsomal enzymes catalyzed the oxidation of o-, m-, and p-tolualdehydes, intermediate metabolites of xylene, to the corresponding toluic acids. Cofactor requirement for the catalytic activity indicates that the microsomes contain NAD- and NADPH-dependent enzymes for this reaction. GC/MS analyses of the carboxylic acids formed by incubation under oxygen-18 gas indicate that the mechanism for this oxidation is an oxygenation and a dehydrogenation for the NADPH- and NAD-dependent reaction. Vmax/Km (nmol/min/mg protein) ratios indicate that the NADPH-dependent activity is more pronounced than the NAD-dependent activity. These results suggest that the NADPH-dependent reaction is mainly responsible for the microsomal oxidation of tolualdehydes. The NADPH-dependent activity was significantly inhibited by SKF 525-A, disulfiram and menadione, inhibitors of cytochrome P450 (P450), suggesting the involvement of P450 in the reaction. In a reconstituted system, P450 MUT-2 (CYP2C29) purified from mouse hepatic microsomes catalyzed the oxidation of o-, m-, and p-tolualdehydes to the carboxylic acids, and the specific activities (nmol/min/nmol P450) were 1.44, 2.81, and 2.32, respectively. Rabbit antibody raised against P450 MUT-2 significantly inhibited the NADPH-dependent oxidation of tolualdehydes to toluic acids by 88% (o-), 63% (m-), and 62% (p-) using mouse hepatic microsomes. The present study demonstrated that a mouse hepatic microsomal aldehyde oxygenase, P450 MUT-2, catalyzed the most of oxidative activity of tolualdehydes to toluic acids in the microsomes.

  14. pH-Dependent reactivity of oxidants formed by iron and copper-catalyzed decomposition of hydrogen peroxide.

    PubMed

    Lee, Hongshin; Lee, Hye-Jin; Sedlak, David L; Lee, Changha

    2013-07-01

    The decomposition of hydrogen peroxide catalyzed by iron and copper leads to the generation of reactive oxidants capable of oxidizing various organic compounds. However, the specific nature of the reactive oxidants is still unclear, with evidence suggesting the production of hydroxyl radical or high-valent metal species. To identify the reactive species in the Fenton system, the oxidation of a series of different compounds (phenol, benzoic acid, methanol, Reactive Black 5 and arsenite) was studied for iron- and copper-catalyzed reactions at varying pH values. At lower pH values, more reactive oxidants appear to be formed in both iron and copper-catalyzed systems. The aromatic compounds, phenol and benzoic acid, were not oxidized under neutral or alkaline pH conditions, whereas methanol, Reactive Black 5, and arsenite were oxidized to a different degree, depending on the catalytic system. The oxidants responsible for the oxidation of compounds at neutral and alkaline pH values are likely to be high-valent metal complexes of iron and copper (i.e., ferryl and cupryl ions).

  15. Controlled aluminum-induced crystallization of an amorphous silicon thin film by using an oxide-layer diffusion barrier

    NASA Astrophysics Data System (ADS)

    Hwang, Ji-Hyun; Kwak, Hyunmin; Kwon, Myeung Hoi

    2014-03-01

    Aluminum-induced crystallization (AIC) of amorphous silicon with an Al2O3 diffusion barrier was investigated for controlling Si crystallization and preventing layer exchange during the annealing process. An Al2O3 layer was deposited between the a-Si and the Al films (a-Si/Al2O3/Al/Glass) and was blasted with an air spray gun with alumina beads to form diffusion channels between the Si and the Al layers. During the annealing process, small grain Si x Al seeds were formed at the channels. Then, the Al2O3 diffusion barrier was restructured to close the channels and prevent further diffusion of Al atoms into the a-Si layer. A polycrystalline Si film with (111), (220) and (311) crystallization peaks in the X-ray diffraction pattern was formed by annealing at 560 °C in a conventional furnace. That film showed a p-type semiconducting behavior with good crystallinity and a large grain size of up to 14.8 µm. No layer conversion occurred between the Si and the Al layers, which had been the fundamental obstacle to the applications in the crystallization of a-Si films by using the AIC method.

  16. Low-resistance magnetic tunnel junctions prepared by partial remote plasma oxidation of 0.9 nm Al barriers

    SciTech Connect

    Ferreira, Ricardo; Freitas, Paulo P.; MacKenzie, Maureen; Chapman, John N.

    2005-05-09

    Current perpendicular to the plane read-head elements suitable for high-density magnetic storage require low resistance while maintaining a reasonable magnetoresistive (MR) signal (RxA<1 {omega} {mu}m{sup 2} and MR>20% for areal densities >200 Gb/in{sup 2}). This letter shows that competitive low RxA junctions can be produced using underoxidized barriers starting from 0.9 nm thick Al layers. For as-deposited junctions, tunneling magnetoresistance (TMR) {approx}20% for RxA{approx}2-15 {omega} {mu}m{sup 2} is obtained, while in the RxA{approx}60-150 {omega} {mu}m{sup 2} range, TMR values between 40% to 45% are achieved. A limited number of junctions exhibits considerably lower RxA values with respect to the average, while keeping a similar MR (down to 0.44 {omega} {mu}m{sup 2} with TMR of 20% and down to 2.2 {omega} {mu}m{sup 2} with TMR of 52%). Experimental data suggest that current confinement to small regions (barrier defects/hot spots) may explain these results.

  17. Self-Adaptive Spike-Time-Dependent Plasticity of Metal-Oxide Memristors

    PubMed Central

    Prezioso, M.; Merrikh Bayat, F.; Hoskins, B.; Likharev, K.; Strukov, D.

    2016-01-01

    Metal-oxide memristors have emerged as promising candidates for hardware implementation of artificial synapses – the key components of high-performance, analog neuromorphic networks - due to their excellent scaling prospects. Since some advanced cognitive tasks require spiking neuromorphic networks, which explicitly model individual neural pulses (“spikes”) in biological neural systems, it is crucial for memristive synapses to support the spike-time-dependent plasticity (STDP). A major challenge for the STDP implementation is that, in contrast to some simplistic models of the plasticity, the elementary change of a synaptic weight in an artificial hardware synapse depends not only on the pre-synaptic and post-synaptic signals, but also on the initial weight (memristor’s conductance) value. Here we experimentally demonstrate, for the first time, an STDP behavior that ensures self-adaptation of the average memristor conductance, making the plasticity stable, i.e. insensitive to the initial state of the devices. The experiments have been carried out with 200-nm Al2O3/TiO2−x memristors integrated into 12 × 12 crossbars. The experimentally observed self-adaptive STDP behavior has been complemented with numerical modeling of weight dynamics in a simple system with a leaky-integrate-and-fire neuron with a random spike-train input, using a compact model of memristor plasticity, fitted for quantitatively correct description of our memristors. PMID:26893175

  18. Iron-dependent oxidative inactivation with affinity cleavage of pyruvate kinase.

    PubMed

    Murakami, Keiko; Tsubouchi, Ryoko; Fukayama, Minoru; Qiao, Shanlou; Yoshino, Masataka

    2009-07-01

    Treatment of rabbit muscle pyruvate kinase with iron/ascorbate caused an inactivation with the cleavage of peptide bond. The inactivation or fragmentation of the enzyme was prevented by addition of Mg2+, catalase, and mannitol, but ADP and PEP the substrates did not show any effect. Protective effect of catalase and mannitol suggests that hydroxyl radical produced through the ferrous ion-dependent reduction of oxygen is responsible for the inactivation/fragmentation of the enzyme. SDS-PAGE and TOF-MS analysis confirmed five pairs of fragments, which were determined to result from the cleavage of the Lys114-Gly115, Glu117-Ile118, Asp177-Gly178, Gly207-Val208, and Phe243-Ile244 bonds of the enzyme by amino-terminal sequencing analysis. Protection of the enzyme by Mg2+ implies the identical binding sites of Fe2+ and Mg2+, but the cleavage sites were discriminated from the cofactor Mg2+-binding sites. Considering amino acid residues interacting with metal ions and tertiary structure, Fe2+ ion may bind to Asp177 neighboring to Gly207 and Glu117 neighboring to Lys114 and Phe243, causing the peptide cleavage by hydroxyl radical. Iron-dependent oxidative inactivation/fragmentation of pyruvate kinase can explain the decreased glycolytic flux under aerobic conditions. Intracellular free Mg2+ concentrations are responsible for the control of cellular respiration and glycolysis.

  19. Applicability of anaerobic nitrate-dependent Fe(II) oxidation to microbial enhanced oil recovery (MEOR).

    PubMed

    Zhu, Hongbo; Carlson, Han K; Coates, John D

    2013-08-06

    Microbial processes that produce solid-phase minerals could be judiciously applied to modify rock porosity with subsequent alteration and improvement of floodwater sweep in petroleum reservoirs. However, there has been little investigation of the application of this to enhanced oil recovery (EOR). Here, we investigate a unique approach of altering reservoir petrology through the biogenesis of authigenic rock minerals. This process is mediated by anaerobic chemolithotrophic nitrate-dependent Fe(II)-oxidizing microorganisms that precipitate iron minerals from the metabolism of soluble ferrous iron (Fe(2+)) coupled to the reduction of nitrate. This mineral biogenesis can result in pore restriction and reduced pore throat diameter. Advantageously and unlike biomass plugs, these biominerals are not susceptible to pressure or thermal degradation. Furthermore, they do not require continual substrate addition for maintenance. Our studies demonstrate that the biogenesis of insoluble iron minerals in packed-bed columns results in effective hydrology alteration and homogenization of heterogeneous flowpaths upon stimulated microbial Fe(2+) biooxidation. We also demonstrate almost 100% improvement in oil recovery from hydrocarbon-saturated packed-bed columns as a result of this metabolism. These studies represent a novel departure from traditional microbial EOR approaches and indicate the potential for nitrate-dependent Fe(2+) biooxidation to improve volumetric sweep efficiency and enhance both the quality and quantity of oil recovered.

  20. Graphene oxide-dependent growth and self-aggregation into a hydrogel complex of exoelectrogenic bacteria

    PubMed Central

    Yoshida, Naoko; Miyata, Yasushi; Doi, Kasumi; Goto, Yuko; Nagao, Yuji; Tero, Ryugo; Hiraishi, Akira

    2016-01-01

    Graphene oxide (GO) is reduced by certain exoelectrogenic bacteria, but its effects on bacterial growth and metabolism are a controversial issue. This study aimed to determine whether GO functions as the terminal electron acceptor to allow specific growth of and electricity production by exoelectrogenic bacteria. Cultivation of environmental samples with GO and acetate as the sole substrate could specifically enrich exoelectrogenic bacteria with Geobacter species predominating (51–68% of the total populations). Interestingly, bacteria in these cultures self-aggregated into a conductive hydrogel complex together with biologically reduced GO (rGO). A novel GO-respiring bacterium designated Geobacter sp. strain R4 was isolated from this hydrogel complex. This organism exhibited stable electricity production at >1000 μA/cm3 (at 200 mV vs Ag/AgCl) for more than 60 d via rGO while temporary electricity production using graphite felt. The better electricity production depends upon the characteristics of rGO such as a large surface area for biofilm growth, greater capacitance, and smaller internal resistance. This is the first report to demonstrate GO-dependent growth of exoelectrogenic bacteria while forming a conductive hydrogel complex with rGO. The simple put-and-wait process leading to the formation of hydrogel complexes of rGO and exoelectrogens will enable wider applications of GO to bioelectrochemical systems. PMID:26899353

  1. Cellular localization and detergent dependent oligomerization of rice allene oxide synthase-1.

    PubMed

    Yoeun, Sereyvath; Kim, Jeong-Il; Han, Oksoo

    2015-01-01

    Allene oxide synthase-1 from Oryza sativa (OsAOS1) localizes to the chloroplast, but lacks a putative chloroplast targeting sequence typically found in dicot AOS. Here, kinetic parameters and the oligomerization state/subunit composition of OsAOS1 were characterized in vitro in the absence or presence of detergent micelles. The catalytic efficiency (k(cat)/K(m)) of OsAOS1 reached a maximum near the critical micelle concentration for polyoxyethylene 10 tridecyl ether. Native gel analysis showed that OsAOS1 exists as a multimer in the absence of detergent micelles. The multimeric form of OsAOS1 was stably cross-linked in the absence of detergents, while only monomeric OsAOS1 was detected in the presence of detergent micelles. Gel filtration analysis indicated that the oligomeric state of OsAOS1 depends strongly on the detergents and that the monomer becomes the predominant form in the presence of detergent micelles. These data suggest that the detergent-dependent oligomeric state of OsAOS1 is an important factor for the regulation of its catalytic efficiency.

  2. Oxidized low-density lipoproteins upregulate proline oxidase to initiate ROS-dependent autophagy.

    PubMed

    Zabirnyk, Olga; Liu, Wei; Khalil, Shadi; Sharma, Anit; Phang, James M

    2010-03-01

    Epidemiological studies showed that high levels of oxidized low-density lipoproteins (oxLDLs) are associated with increased cancer risk. We examined the direct effect of physiologic concentrations oxLDL on cancer cells. OxLDLs were cytotoxic and activate both apoptosis and autophagy. OxLDLs have ligands for peroxisome proliferator-activated receptor gamma and upregulated proline oxidase (POX) through this nuclear receptor. We identified 7-ketocholesterol (7KC) as a main component responsible for the latter. To elucidate the role of POX in oxLDL-mediated cytotoxicity, we knocked down POX via small interfering RNA and found that this (i) further reduced viability of cancer cells treated with oxLDL; (ii) decreased oxLDL-associated reactive oxygen species generation; (iii) decreased autophagy measured via beclin-1 protein level and light-chain 3 protein (LC3)-I into LC3-II conversion. Using POX-expressing cell model, we established that single POX overexpression was sufficient to activate autophagy. Thus, it led to autophagosomes accumulation and increased conversion of LC3-I into LC3-II. Moreover, beclin-1 gene expression was directly dependent on POX catalytic activity, namely the generation of POX-dependent superoxide. We conclude that POX is critical in the cellular response to the noxious effects of oxLDL by activating protective autophagy.

  3. Dependence of the critical temperature in overdoped copper oxides on superfluid density

    DOE PAGES

    Božović, I.; He, X.; Wu, J.; ...

    2016-08-17

    The physics of underdoped copper-oxide superconductors, including the pseudogap, spin and charge ordering, and their relation to superconductivity1-3, is intensely debated. The overdoped side is perceived as simpler, with strongly-correlated fermion physics evolving smoothly into the conventional Bardeen-Cooper-Schrieffer (BCS) behavior. Pioneering studies on a few overdoped samples4-11 indicated that the superfluid density was much smaller than expected, but this was attributed to pair-breaking, disorder, and phase separation. Here, we test this conjecture by studying how the magnetic penetration depth λ and the phase stiffness ρs depend on temperature and doping, scanning densely the entire overdoped side of the La2-xSrxCuO4 (LSCO)more » phase diagram. We have measured the absolute values of λ and ρs to the accuracy of ±1% in thousands of cuprate samples; the large statistics reveals clear trends and intrinsic properties. The films are quite homogeneous; variations in the critical temperature (Tc) within a film are very small (< 1 K). At every doping, ρs(T) decreases linearly with temperature. The Tc(ρ s0) dependence is linear but with an offset, (Tc - T0) ∝ ρs0 where T0 ≈ 7 K, except very close to the origin where Tc ∝ √ρ s0. This scaling law defies the standard BCS description, posing a challenge to theory.« less

  4. A new approach to the non-oxidative conversion of gaseous alkanes in a barrier discharge and features of the reaction mechanism

    NASA Astrophysics Data System (ADS)

    Kudryashov, S.; Ryabov, A.; Shchyogoleva, G.

    2016-01-01

    A new approach to the non-oxidative conversion of C1-C4 alkanes into gaseous and liquid products in a barrier discharge is proposed. It consists in inhibiting the formation of deposits on the reactor electrode surfaces due to the addition of distilled water into the flow of hydrocarbon gases. The energy consumption on hydrocarbon conversion decreases from methane to n-butane from ~46 to 35 eV molecule-1. The main gaseous products of the conversion of light alkanes are hydrogen and C2-C4 hydrocarbons. The liquid reaction products contain C5+ alkanes with a predominantly isomeric structure. The results of modeling the kinetics of chemical reactions show that an increase in the molecular weight of the reaction products is mainly due to processes involving CH2 radical and the recombination of alkyl radicals.

  5. Gas-Barrier Hybrid Coatings by the Assembly of Novel Poly(vinyl alcohol) and Reduced Graphene Oxide Layers through Cross-Linking with Zirconium Adducts.

    PubMed

    Yan, Ning; Capezzuto, Filomena; Buonocore, Giovanna G; Lavorgna, Marino; Xia, Hesheng; Ambrosio, Luigi

    2015-10-14

    Gas-barrier materials obtained by coating poly(ethylene terephthalate) (PET) substrates have already been studied in the recent literature. However, because of the benefits of using cheaper, biodegradable, and nonpolar polymers, multilayered hybrid coatings consisting of alternate layers of reduced graphene oxide (rGO) nanosheets and a novel high amorphous vinyl alcohol (HAVOH) with zirconium (Zr) adducts as binders were successfully fabricated through a layer-by-layer (LbL) assembly approach. Atomic force microscopy analysis showed that rGO nanoplatelets were uniformly dispersed over the HAVOH polymer substrate. Scanning and transmission electron microscopies revealed that multilayer (HAVOH/Zr/rGO)n hybrid coatings exhibited a brick-wall structure with HAVOH and rGO as buildings blocks. It has been shown that 40 layers of HAVOH/Zr/rGO ultrathin films deposited on PET substrates lead to a decrease of 1 order of magnitude of oxygen permeability with respect to the pristine PET substrate. This is attributed to the effect of zirconium polymeric adducts, which enhance the assembling efficiency of rGO and compact the layers, as confirmed by NMR characterization, resulting in a significant increment of the oxygen-transport pathways. Because of their high barrier properties and high flexibility, these films are promising candidates in a variety of applications such as packaging, selective gas films, and protection of flexible electronics.

  6. Physicochemical properties of iron oxide nanoparticles that contribute to cellular ROS-dependent signaling and acellular production of hydroxyl radical.

    PubMed

    Vogel, Christoph F A; Charrier, Jessica G; Wu, Dalei; McFall, Alexander S; Li, Wen; Abid, Aamir; Kennedy, Ian M; Anastasio, Cort

    2016-01-01

    While nanoparticles (NPs) are increasingly used in a variety of consumer products and medical applications, some of these materials have potential health concerns. Macrophages are the primary responders to particles that initiate oxidative stress and inflammatory reactions. Here, we utilized six flame-synthesized, engineered iron oxide NPs with various physicochemical properties (e.g. Fe oxidation state and crystal size) to study their interactions with RAW 264.7 macrophages, their iron solubilities, and their abilities to produce hydroxyl radical in an acellular assay. Both iron solubility and hydroxyl radical production varied between NPs depending on crystalline diameter and surface area of the particles, but not on iron oxidation state. Macrophage treatment with the iron oxide NPs showed a dose-dependent increase of heme oxygenase 1 (HO-1) and NAD(P)H:quinone oxidoreductase (NQO-1). The nuclear factor (NF)-erythroid-derived 2 (E2)-related factor 2 (Nrf2) modulates the transcriptional activity of antioxidant response element (ARE)-driven genes, such as HO-1 and NQO-1. Here, we show that the iron oxide NPs activate Nrf2, leading to its increased nuclear accumulation and enhanced Nrf2 DNA-binding activity in NP-treated RAW 264.7 macrophages. Iron solubility and acellular hydroxyl radical generation depend on the physical properties of the NPs, especially crystalline diameter; however, these properties are weakly linked to the activation of cellular signaling of Nrf2 and the expression of oxidative stress markers. Overall, our work shows for the first time that iron oxide nanoparticles induce cellular marker genes of oxidative stress and that this effect is transcriptionally mediated through the Nrf2-ARE signaling pathway in macrophages.

  7. Thermal barrier coating system

    NASA Technical Reports Server (NTRS)

    Stecura, S. (Inventor)

    1984-01-01

    A high temperature oxidation resistant, thermal barrier coating system is disclosed for a nickel cobalt, or iron base alloy substrate. An inner metal bond coating contacts the substrate, and a thermal barrier coating covers the bond coating. NiCrAlR, FeCrAlR, and CoCrAlR alloys are satisfactory as bond coating compositions where R=Y or Yb. These alloys contain, by weight, 24.9-36.7% chromium, 5.4-18.5% aluminum, and 0.05 to 1.55% yttrium or 0.05 to 0.53% ytterbium. The coatings containing ytterbium are preferred over those containing yttrium. An outer thermal barrier coating of partial stabilized zirconium oxide (zirconia) which is between 6% and 8%, by weight, of yttrium oxide (yttria) covers the bond coating. Partial stabilization provides a material with superior durability. Partially stabilized zirconia consists of mixtures of cubic, tetragonal, and monoclinic phases.

  8. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    SciTech Connect

    O'Day, Peggy A.; Asta, Maria P.; Kanematsu, Masakazu; Beller, Harry; Zhou, Peng; Steefel, Carl

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  9. Modeling on oxide dependent 2DEG sheet charge density and threshold voltage in AlGaN/GaN MOSHEMT

    NASA Astrophysics Data System (ADS)

    Panda, J.; Jena, K.; Swain, R.; Lenka, T. R.

    2016-04-01

    We have developed a physics based analytical model for the calculation of threshold voltage, two dimensional electron gas (2DEG) density and surface potential for AlGaN/GaN metal oxide semiconductor high electron mobility transistors (MOSHEMT). The developed model includes important parameters like polarization charge density at oxide/AlGaN and AlGaN/GaN interfaces, interfacial defect oxide charges and donor charges at the surface of the AlGaN barrier. The effects of two different gate oxides (Al2O3 and HfO2) are compared for the performance evaluation of the proposed MOSHEMT. The MOSHEMTs with Al2O3 dielectric have an advantage of significant increase in 2DEG up to 1.2 × 1013 cm-2 with an increase in oxide thickness up to 10 nm as compared to HfO2 dielectric MOSHEMT. The surface potential for HfO2 based device decreases from 2 to -1.6 eV within 10 nm of oxide thickness whereas for the Al2O3 based device a sharp transition of surface potential occurs from 2.8 to -8.3 eV. The variation in oxide thickness and gate metal work function of the proposed MOSHEMT shifts the threshold voltage from negative to positive realizing the enhanced mode operation. Further to validate the model, the device is simulated in Silvaco Technology Computer Aided Design (TCAD) showing good agreement with the proposed model results. The accuracy of the developed calculations of the proposed model can be used to develop a complete physics based 2DEG sheet charge density and threshold voltage model for GaN MOSHEMT devices for performance analysis.

  10. Novel tunnelling barriers for spin tunnelling junctions

    NASA Astrophysics Data System (ADS)

    Sharma, Manish

    A tunnel junction consists of two metal electrodes separated by an insulating barrier thin enough for electrons to tunnel across. With ferromagnetic electrodes, a spin-dependent tunnelling (SDT) effect, electrons of one spin tunnelling preferentially over those of the other, is observed. When the electrodes are switched from a parallel to an anti-parallel alignment, the tunnelling current changes and gives rise to tunnelling magnetoresistance (TMR). Since 1995, interest in SDT junctions has increased as TMR in excess of 15% has been achieved, making viable their use in non-volatile memory and magnetic sensors applications. In this work, two key issues of SDT junctions are addressed: spin polarization of the electrode and the tunnel barrier. Spin polarization, a measure of electron states of up and down spins, is widely believed to be an intrinsic property of the electrode. In junctions with barriers formed by plasma oxidation of composite Ta/Al films, the surprising effect of the resistance being lower with the electrodes aligned antiparallel was observed. Junctions with Ta/Al barriers and those with Al/Ta barriers behave opposite to each other and exhibit an inversion only when the Ta side of the barrier is biased positive. This demonstrates the spin polarization is also influenced by the barrier material. Half-metallic materials such as magnetite (Fe3O4) have a gap in one of the spins' states at the fermi level, thus having a theoretical spin polarization of 100%. In this work, an ultrathin Fe3O 4 layer was added between the Al2O3 barrier and the NiFe electrode. The TMR increased sharply from 4% to 16% for thicknesses less than 0.5nm. As the tunnel barrier must be thinner than 2nm, choice of the barrier material becomes critical. Presently, Al2O3 is the best known barrier. In looking for alternative materials, AlN and AlON were formed by plasma nitridation and oxy-nitridation of deposited Al films. TMR results of up to 18% and resistance-area products down to 3

  11. The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy

    PubMed Central

    House, Christopher H.; Beal, Emily J.; Orphan, Victoria J.

    2011-01-01

    On Earth, marine anaerobic methane oxidation (AOM) can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2) found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to release), a total

  12. Deltamethrin-induced oxidative stress and mitochondrial caspase-dependent signaling pathways in murine splenocytes.

    PubMed

    Kumar, Anoop; Sasmal, D; Bhaskar, Amand; Mukhopadhyay, Kunal; Thakur, Aman; Sharma, Neelima

    2016-07-01

    Deltamethrin (DLM) is a well-known pyrethroid insecticide used extensively in pest control. Exposure to DLM has been demonstrated to cause apoptosis in various cells. However, the immunotoxic effects of DLM on mammalian system and its mechanism is still an open question to be explored. To explore these effects, this study has been designed to first observe the interactions of DLM to immune cell receptors and its effects on the immune system. The docking score revealed that DLM has strong binding affinity toward the CD45 and CD28 receptors. In vitro study revealed that DLM induces apoptosis in murine splenocytes in a concentration-dependent manner. The earliest markers of apoptosis such as enhanced reactive oxygen species and caspase 3 activation are evident as early as 1 h by 25 and 50 µM DLM. Western blot analysis demonstrated that p38 MAP kinase and Bax expression is increased in a concentration-dependent manner, whereas Bcl 2 expression is significantly reduced after 3 h of DLM treatment. Glutathione depletion has been also observed at 3 and 6 h by 25 and 50 µM concentration of DLM. Flow cytometry results imply that the fraction of hypodiploid cells has gradually increased with all the concentrations of DLM at 18 h. N-acetyl cysteine effectively reduces the percentage of apoptotic cells, which is increased by DLM. In contrast, buthionine sulfoxamine causes an elevation in the percentage of apoptotic cells. Phenotyping data imply the effect of DLM toxicity in murine splenocytes. In brief, the study demonstrates that DLM causes apoptosis through its interaction with CD45 and CD28 receptors, leading to oxidative stress and activation of the mitochondrial caspase-dependent pathways which ultimately affects the immune functions. This study provides mechanistic information by which DLM causes toxicity in murine splenocytes. © 2014 Wiley Periodicals, Inc. Environ Toxicol 31: 808-819, 2016.

  13. Nitric Oxide Mediates Activity-Dependent Plasticity of Retinal Bipolar Cell Output via S-Nitrosylation

    PubMed Central

    Tooker, Ryan E.; Lipin, Mikhail Y.; Leuranguer, Valerie; Rozsa, Eva; Bramley, Jayne R.; Harding, Jacqueline L.; Reynolds, Melissa M.

    2013-01-01

    Coding a wide range of light intensities in natural scenes poses a challenge for the retina: adaptation to bright light should not compromise sensitivity to dim light. Here we report a novel form of activity-dependent synaptic plasticity, specifically, a “weighted potentiation” that selectively increases output of Mb-type bipolar cells in the goldfish retina in response to weak inputs but leaves the input–output ratio for strong stimuli unaffected. In retinal slice preparation, strong depolarization of bipolar terminals significantly lowered the threshold for calcium spike initiation, which originated from a shift in activation of voltage-gated calcium currents (ICa) to more negative potentials. The process depended upon glutamate-evoked retrograde nitric oxide (NO) signaling as it was eliminated by pretreatment with an NO synthase blocker, TRIM. The NO-dependent ICa modulation was cGMP independent but could be blocked by N-ethylmaleimide (NEM), indicating that NO acted via an S-nitrosylation mechanism. Importantly, the NO action resulted in a weighted potentiation of Mb output in response to small (≤−30 mV) depolarizations. Coincidentally, light flashes with intensity ≥2.4 × 108 photons/cm2/s lowered the latency of scotopic (≤2.4 × 108 photons/cm2/s) light-evoked calcium spikes in Mb axon terminals in an NEM-sensitive manner, but light responses above cone threshold (≥3.5 × 109 photons/cm2/s) were unaltered. Under bright scotopic/mesopic conditions, this novel form of Mb output potentiation selectively amplifies dim retinal inputs at Mb → ganglion cell synapses. We propose that this process might counteract decreases in retinal sensitivity during light adaptation by preventing the loss of visual information carried by dim scotopic signals. PMID:24305814

  14. Nitric Oxide Donors Enhance the Frequency Dependence of Dopamine Release in Nucleus Accumbens

    PubMed Central

    Hartung, Henrike; Threlfell, Sarah; Cragg, Stephanie J

    2011-01-01

    Dopamine (DA) neurotransmission in the nucleus accumbens (NAc) is critically involved in normal as well as maladaptive motivated behaviors including drug addiction. Whether the striatal neuromodulator nitric oxide (NO) influences DA release in NAc is unknown. We investigated whether exogenous NO modulates DA transmission in NAc core and how this interaction varies depending on the frequency of presynaptic activation. We detected DA with cyclic voltammetry at carbon-fiber microelectrodes in mouse NAc in slices following stimuli spanning a full range of DA neuron firing frequencies (1–100 Hz). NO donors 3-morpholinosydnonimine hydrochloride (SIN-1) or z-1-[N-(3-ammoniopropyl)-N-(n-propyl)amino]diazen-1-ium-1,2-diolate (PAPA/NONOate) enhanced DA release with increasing stimulus frequency. This NO-mediated enhancement of frequency sensitivity of DA release was not prevented by inhibition of soluble guanylyl cyclase (sGC), DA transporters, or large conductance Ca2+-activated K+ channels, and did not require glutamatergic or GABAergic input. However, experiments to identify whether frequency-dependent NO effects were mediated via changes in powerful acetylcholine–DA interactions revealed multiple components to NO modulation of DA release. In the presence of a nicotinic receptor antagonist (dihydro-β-erythroidine), NO donors increased DA release in a frequency-independent manner. These data suggest that NO in the NAc can modulate DA release through multiple GC-independent neuronal mechanisms whose net outcome varies depending on the activity in DA neurons and accumbal cholinergic interneurons. In the presence of accumbal acetylcholine, NO promotes the sensitivity of DA release to presynaptic activation, but with reduced acetylcholine input, NO will promote DA release in an activity-independent manner through a direct action on dopaminergic terminals. PMID:21508928

  15. Diffusion barriers

    NASA Technical Reports Server (NTRS)

    Nicolet, M. A.

    1983-01-01

    The choice of the metallic film for the contact to a semiconductor device is discussed. One way to try to stabilize a contact is by interposing a thin film of a material that has low diffusivity for the atoms in question. This thin film application is known as a diffusion barrier. Three types of barriers can be distinguished. The stuffed barrier derives its low atomic diffusivity to impurities that concentrate along the extended defects of a polycrystalline layer. Sacrificial barriers exploit the fact that some (elemental) thin films react in a laterally uniform and reproducible fashion. Sacrificial barriers have the advantage that the point of their failure is predictable. Passive barriers are those most closely approximating an ideal barrier. The most-studied case is that of sputtered TiN films. Stuffed barriers may be viewed as passive barriers whose low diffusivity material extends along the defects of the polycrystalline host.

  16. TiO2 crystal facet-dependent antimony adsorption and photocatalytic oxidation.

    PubMed

    Song, Jiaying; Yan, Li; Duan, Jinming; Jing, Chuanyong

    2017-02-24

    Anatase TiO2 crystal facets are garnering increasing attention due to their unique surface property. However, no specific linear relationship had been derived between the facet exposed on TiO2 and the surface adsorption capacity as well as photocatalytic performance. This study systematically explored the facet effects on antimony (Sb) adsorption and photocatalytic oxidation using high-index {201} and low-index {101}, {001}, and {100} TiO2. The results suggest that high-index {201} TiO2 exhibits the best Sb(III) adsorption and photocatalytic activity compared to the low-index TiO2. Both the Sb(III) adsorption density and the amount of OH and O2(-) generated in solution were correlated to the magnitude of surface energy on TiO2 facets. Photocatalytically generated OH and O2(-) were responsible for Sb(III) photooxidation as evidenced by radical-trapping experiments. The great contribution of OH was observed only on {201}, not on low-index TiO2. This phenomenon was found to be attributable to the high surface energy on {201}, which enables the generation of a large amount of photogeneration OH to compensate for the fast rate of OH dissipation. Therefore, the predominant participation of OH in Sb(III) photooxidation was only possible on high-index {201} TiO2, which resulted in an enhanced photocatalytic rate. On the other hand, O2(-) dominated the Sb(III) photocatalytic oxidation on low-index TiO2. The intrinsic facet-dependent adsorption and photocatalytic mechanism obtained from this study would be useful for developing TiO2-based environmental technologies.

  17. Mas receptor is involved in the estrogen-receptor induced nitric oxide-dependent vasorelaxation.

    PubMed

    Sobrino, Agua; Vallejo, Susana; Novella, Susana; Lázaro-Franco, Macarena; Mompeón, Ana; Bueno-Betí, Carlos; Walther, Thomas; Sánchez-Ferrer, Carlos; Peiró, Concepción; Hermenegildo, Carlos

    2017-04-01

    The Mas receptor is involved in the angiotensin (Ang)-(1-7) vasodilatory actions by increasing nitric oxide production (NO). We have previously demonstrated an increased production of Ang-(1-7) in human umbilical vein endothelial cells (HUVEC) exposed to estradiol (E2), suggesting a potential cross-talk between E2 and the Ang-(1-7)/Mas receptor axis. Here, we explored whether the vasoactive response and NO-related signalling exerted by E2 are influenced by Mas. HUVEC were exposed to 10nM E2 for 24h in the presence or absence of the selective Mas receptor antagonist A779, and the estrogen receptor (ER) antagonist ICI182780 (ICI). E2 increased Akt and endothelial nitric oxide synthase (eNOS) mRNA and protein expression, measured by RT-PCR and Western blot, respectively. Furthermore, E2 increased Akt activity (determined by the levels of phospho-Ser(473)) and eNOS activity (by the enhanced phosphorylation of Ser(1177), the activated form), resulting in increased NO production, which was measured by the fluorescence probe DAF-2-FM. These signalling events were dependent on ER and Mas receptor activation, since they were abolished in the presence of ICI or A779. In ex-vivo functional experiments performed with a small-vessel myograph in isolated mesenteric vessels from wild-type mice pre-contracted with noradrenaline, the relaxant response to physiological concentrations of E2 was blocked by ICI and A779, to the same extent to that obtained in the vessels isolated from Mas-deficient. In conclusion, E2 induces NO production and vasodilation through mechanisms that require Mas receptor activation.

  18. Neonatal oxidative stress depends on oxygen blood pressure in umbilical artery.

    PubMed

    Proietti, F; De Bernardo, G; Longini, M; Sordino, D; Scaramuzzini, G; Tataranno, M L; Belvisi, E; Bazzini, F; Perrone, S; Buonocore, G

    2016-01-01

    With advancing gestation, partial pressure of oxygen (pO2) and pH fall significantly. Hypoxia is a main factor inducing free radical generation and thereby oxidative stress (OS). Placental and fetal tissue response when oxygen becomes restricted is complex and partially known. We tested the hypothesis that changes in umbilical artery and vein blood gas concentrations modulate OS occurrence in the newborn. Seventy umbilical artery and vein plasma samples were collected from healthy term newborns immediately after delivery. F2 Isoprostanes (F2-Isop) were measured in all samples as reliable markers of lipid peroxidation. Significantly lower pCO2 and higher pO2 and pH were found in umbilical vein than in artery, as expected. A positive correlation was detected between pH and pO2 only in umbilical artery (p=0.019). F2-Isop levels were no different between artery and vein in cord blood. Significant correlations were found between F2-Isop and pCO2 (p=0.025) as well as between F2-Isop and pH in umbilical vein (p=0.027). F2-Isop correlated with pCO2 (p=0.007) as well as with pO2 values (p=0.005) in umbilical artery blood. Oxidative stress (OS) in newborns depends on oxygen concentrations in umbilical artery. OS biomarkers significantly correlate with pO2 and in umbilical artery but not in umbilical vein. In normoxic conditions fetal-maternal gas exchanges occurring in placenta re-establish normal higher oxygen levels in umbilical vein than artery, with a normal production of free radicals without any deleterious effects.

  19. Andrographis paniculata ameliorates carbon tetrachloride (CCl(4))-dependent hepatic damage and toxicity: diminution of oxidative stress.

    PubMed

    Koh, Pei Hoon; Mokhtar, Ruzaidi Azli Mohd; Iqbal, Mohammad

    2011-01-01

    Andrographis paniculata (hempedu bumi) is a plant that possesses many medicinal values in treating several diseases and for health care maintenance. However, its hepatoprotective activity and mechanism of action have not been fully investigated. Therefore, this study aimed to evaluate the hepatoprotective effects of A. paniculata and its mechanism of action in rats. Carbon tetrachloride (CCl(4)) challenge of rats at a dose of 1.2 ml/kg body weight-induced oxidative stress in the liver. This was evidenced by augmentation in lipid peroxidation, which was accompanied by a decrease in the activities of antioxidant enzymes and depletion in the level of reduced glutathione (P < 0.05). Parrallel to these changes, CCl(4) challenge too, enhanced hepatic damage as evidenced by sharp increase in serum transaminases (e.g. alanine aminotransferase, aspartate aminotransferase, and lactate dehydrogenase) (P < 0.05). Additionally, the impairment of liver function corresponded to histolopathological changes. However, most of these changes were reversed in a dose-dependent fashion by pre-treatment of animals with A. paniculata (P < 0.05). The ability of A. paniculata to scavenge the 2,2-Diphenyl-2-picrylhydrazyl radical was determined through its EC(50) value. The EC(50) value of A. paniculata was 583.60 ± 4.25 µg/ml. In addition, A. paniculata was found to contain 65.37 ± 1.20 mg/g total phenolics expressed as gallic acid equivalent. From these studies, it is concluded that A. paniculata could be used as a hepatoprotective agent and possesses the potential to treat or prevent degenerative diseases where oxidative stress is implicated.

  20. Thermal barrier coating system

    NASA Technical Reports Server (NTRS)

    Stecura, S.; Leibert, C. H. (Inventor)

    1977-01-01

    A coating system which contains a bond coating and a thermal barrier coating is applied to metal surfaces such as turbine blades and provides both low thermal conductivity and improved adherence when exposed to high temperature gases or liquids. The bond coating contains NiCrAlY and the thermal barrier coating contains a reflective oxide. The reflective oxides ZrO2-Y2O3 and ZrO2-MgO have demonstrated significant utility in high temperature turbine applications.

  1. Oxidative Stress Increases the Blood Brain Barrier Permeability Resulting in Increased Incidence of Brain Metastasis in BRCA Mutation Carriers

    DTIC Science & Technology

    2014-08-01

    permeability and integrity of the brain endothelium using in vitro and in vivo models. 3) Determine the protective effects of PARP inhibitors and/or selenium ...in preventing BBB-induced damage by oxidative stress, and in inhibiting breast cancer metastasis to the brain. Further, since selenium has anti...inhibitor and ROS inhibitor of BMEC-TJs HBMEC cocultures were preincubated with PARP inhibitor (30mM) or with ROS inhibitor (10mM selenium ) for 6

  2. Impaired OMA1-dependent cleavage of OPA1 and reduced DRP1 fission activity combine to prevent mitophagy in cells that are dependent on oxidative phosphorylation

    PubMed Central

    MacVicar, Thomas D. B.; Lane, Jon D.

    2014-01-01

    ABSTRACT Mitochondrial dynamics play crucial roles in mitophagy-based mitochondrial quality control, but how these pathways are regulated to meet cellular energy demands remains obscure. Using non-transformed human RPE1 cells, we report that upregulation of mitochondrial oxidative phosphorylation alters mitochondrial dynamics to inhibit Parkin-mediated mitophagy. Despite the basal mitophagy rates remaining stable upon the switch to dependence on oxidative phosphorylation, mitochondria resist fragmentation when RPE1 cells are treated with the protonophore carbonyl cyanide m-chlorophenyl hydrazone. Mechanistically, we show that this is because cleavage of the inner membrane fusion factor L-OPA1 is prevented due to the failure to activate the inner membrane protease OMA1 in mitochondria that have a collapsed membrane potential. In parallel, mitochondria that use oxidative phosphorylation are protected from damage-induced fission through the impaired recruitment and activation of mitochondrial DRP1. Using OMA1-deficient MEF cells, we show that the preservation of a stable pool of L-OPA1 at the inner mitochondrial membrane is sufficient to delay mitophagy, even in the presence of Parkin. The capacity of cells that are dependent on oxidative phosphorylation to maintain substantial mitochondrial content in the face of acute damage has important implications for mitochondrial quality control in vivo. PMID:24634514

  3. Oxidative stress pathways involved in cytotoxicity and genotoxicity of titanium dioxide (TiO2) nanoparticles on cells constitutive of alveolo-capillary barrier in vitro.

    PubMed

    Hanot-Roy, Maïté; Tubeuf, Emilie; Guilbert, Ariane; Bado-Nilles, Anne; Vigneron, Pascale; Trouiller, Bénédicte; Braun, Anne; Lacroix, Ghislaine

    2016-06-01

    The health risks of nanoparticles remain a serious concern given their prevalence from industrial and domestic use. The primary route of titanium dioxide nanoparticle exposure is inhalation. The extent to which nanoparticles contribute to cellular toxicity is known to associate induction of oxidative stress. To investigate this problem further, the effect of titanium dioxide nanoparticles was examined on cell lines representative of alveolo-capillary barrier. The present study showed that all nanoparticle-exposed cell lines displayed ROS generation. Macrophage-like THP-1 and HPMEC-ST1.6R microvascular cells were sensitive to endogenous redox changes and underwent apoptosis, but not alveolar epithelial A549 cells. Genotoxic potential of titanium dioxide nanoparticles was investigated using the activation of γH2AX, activation of DNA repair proteins and cell cycle arrest. In the sensitive cell lines, DNA damage was persistent and activation of DNA repair pathways was observed. Moreover, western blot analysis showed that specific pathways associated with cellular stress response were activated concomitantly with DNA repair or apoptosis. Nanoparticles-induced oxidative stress is finally signal transducer for further physiological effects including genotoxicity and cytotoxicity. Within activated pathways, HSP27 and SAPK/JNK proteins appeared as potential biomarkers of intracellular stress and of sensitivity to endogenous redox changes, respectively, enabling to predict cell behavior.

  4. Nitrous oxide persistently alleviates pain hypersensitivity in neuropathic rats: A dose-dependent effect

    PubMed Central

    Ben Boujema, Meric; Laboureyras, Emilie; Pype, Jan; Bessière, Baptiste; Simonnet, Guy

    2015-01-01

    BACKGROUND: Despite numerous pharmacological approaches, there are no common analgesic drugs that produce meaningful relief for the majority of patients with neuropathic pain. Although nitrous oxide (N2O) is a weak analgesic that acts via opioid-dependent mechanisms, it is also an antagonist of the N-methyl-D-aspartate receptor (NMDAR). The NMDAR plays a critical role in the development of pain sensitization induced by nerve injury. OBJECTIVE: Using the chronic constriction injury of the sciatic nerve in male rats as a preclinical model of neuropathic pain, the first aim of the present study was to evaluate the lowest N2O concentration and the shortest time of N2O postinjury exposure that would produce persistent relief of neuropathic pain. The second aim was to compare the effects of N2O with gabapentin, a reference drug used in human neuropathic pain relief. METHODS: Changes in the nociceptive threshold were evaluated using the paw pressure vocalization test in rats. RESULTS: Among the various N2O concentrations tested, which ranged from 25% to 50%, only 50% N2O single exposure for 1 h 15 min induced a persistent (minimum of three weeks) and significant (60%) reduction in pain hypersensitivity. A single gabapentin dose (75 mg/kg to 300 mg/kg, intraperitoneally) induced an acute (1 h to 1 h 30 min) dose-dependent effect, but not a persistent effect such as that observed with N2O. CONCLUSIONS: These preclinical results suggest that N2O is advantageous for long-lasting neuropathic pain relief after sciatic nerve injury compared with other drugs used in humans such as gabapentinoids or NMDAR antagonists. The present preclinical study provides a rationale for developing comparative clinical studies. PMID:26371891

  5. Integrins mediate mechanical compression-induced endothelium-dependent vasodilation through endothelial nitric oxide pathway.

    PubMed

    Lu, Xiao; Kassab, Ghassan S

    2015-09-01

    Cardiac and skeletal muscle contraction lead to compression of intramuscular arterioles, which, in turn, leads to their vasodilation (a process that may enhance blood flow during muscle activity). Although endothelium-derived nitric oxide (NO) has been implicated in compression-induced vasodilation, the mechanism whereby arterial compression elicits NO production is unclear. We cannulated isolated swine (n = 39) myocardial (n = 69) and skeletal muscle (n = 60) arteriole segments and exposed them to cyclic transmural pressure generated by either intraluminal or extraluminal pressure pulses to simulate compression in contracting muscle. We found that the vasodilation elicited by internal or external pressure pulses was equivalent; moreover, vasodilation in response to pressure depended on changes in arteriole diameter. Agonist-induced endothelium-dependent and -independent vasodilation was used to verify endothelial and vascular smooth muscle cell viability. Vasodilation in response to cyclic changes in transmural pressure was smaller than that elicited by pharmacological activation of the NO signaling pathway. It was attenuated by inhibition of NO synthase and by mechanical removal of the endothelium. Stemming from previous observations that endothelial integrin is implicated in vasodilation in response to shear stress, we found that function-blocking integrin α5β1 or αvβ3 antibodies attenuated cyclic compression-induced vasodilation and NOx (NO(-)2 and NO(-)3) production, as did an RGD peptide that competitively inhibits ligand binding to some integrins. We therefore conclude that integrin plays a role in cyclic compression-induced endothelial NO production and thereby in the vasodilation of small arteries during cyclic transmural pressure loading.

  6. Precipitants of hepatic encephalopathy induce rapid astrocyte swelling in an oxidative stress dependent manner.

    PubMed

    Lachmann, Vera; Görg, Boris; Bidmon, Hans Jürgen; Keitel, Verena; Häussinger, Dieter

    2013-08-15

    Hepatic encephalopathy (HE) is seen as the clinical manifestation of a low grade cerebral edema with formation of reactive oxygen and nitrogen species (RNOS). Astrocyte swelling is a crucial event and in cultured astrocytes HE-relevant factors almost instantaneously induce the formation of RNOS. However, short term effects of ammonia, inflammatory cytokines and RNOS on the volume of astrocytes and other brain cells as well as the underlying mechanisms are largely unknown, although a pathogenic link between RNOS formation and swelling in HE has been proposed. This issue was addressed in the present study by means of live-cell volume microscopy of brain cells in vitro. Ammonia, diazepam and pro-inflammatory cytokines such as tumor-necrosis factor-α (TNF-α), interferon-γ, interleukin-1β induced within 20min astrocyte swelling by about 25% accompanied by nuclear swelling of similar magnitude. Astrocyte swelling in response to NH4Cl, TNF-α or diazepam was abolished by the antioxidant epigallocatechin-gallate pointing to an involvement of RNOS. NH4Cl-induced astrocyte swelling was sensitive to inhibition of glutamine synthetase, NADPH oxidase or nitric oxide synthases. In line with a NMDA receptor-, prostanoid- and Ca(2+)-dependence of NH4Cl-induced RNOS formation, Ca(2+) chelation and inhibition of NMDA receptors or cyclooxygenase suppressed NH4Cl-induced astrocyte swelling, whereas the Ca(2+)-ionophore ionomycin, NMDA, glutamate and prostanoids induced rapid astrocyte swelling. NH4Cl also induced swelling of cultured microglia in a glutamine-synthesis dependent way, but had no effect on cell volume of cultured neurons. It is concluded that the pathways which trigger RNOS formation in astrocytes also trigger astrocyte swelling, whereas conversely and as shown previously hypoosmotic astrocyte swelling can induce RNOS formation. This establishes a complex interplay with an auto-amplificatory loop between RNOS formation and astrocyte swelling as an important event in

  7. Oxidative stress is involved in age-dependent spermatogenic damage of Immp2l mutant mice.

    PubMed

    George, Sunil K; Jiao, Yan; Bishop, Colin E; Lu, Baisong

    Mitochondrial reactive oxygen species (ROS) have been implicated in spermatogenic damage, although direct in vivo evidence is lacking. We recently generated a mouse in which the inner mitochondrial membrane peptidase 2-like (Immp2l) gene is mutated. This Immp2l mutation impairs the processing of signal peptide sequences from mitochondrial cytochrome c₁ and glycerol phosphate dehydrogenase 2. The mitochondria from mutant mice generate elevated levels of superoxide ion, which causes age-dependent spermatogenic damage. Here we confirm age-dependent spermatogenic damage in a new cohort of mutants, which started at the age of 10.5 months. Compared with age-matched controls, protein carbonyl content was normal in testes of 2- to 5-month-old mutants, but significantly elevated in testes of 13-month-old mutants, indicating elevated oxidative stress in the testes at the time of impaired spermatogenesis. Testicular expression of superoxide dismutases was not different between control and mutant mice, whereas that of catalase was increased in young and old mutants. The expression of cytosolic glutathione peroxidase 4 (phospholipid hydroperoxidase) in testes was significantly reduced in 13-month-old mutants, concomitant with impaired spermatogenesis. Apoptosis of all testicular populations was increased in mutant mice with spermatogenic damage. The mitochondrial DNA (mtDNA) mutation rate in germ cells of mutant mice with impaired spermatogenesis was unchanged, excluding a major role of mtDNA mutation in ROS-mediated spermatogenic damage. Our data show that increased mitochondrial ROS are one of the driving forces for spermatogenic impairment.

  8. Upregulation of macrophage-specific functions by oxidized LDL: lysosomal degradation-dependent and -independent pathways.

    PubMed

    Radhika, A; Sudhakaran, P R

    2013-01-01

    Formation of foam cells from macrophages, which are formed by the differentiation of blood-borne monocytes, is a critical early event in atherogenesis. To examine how pre-exposure of monocytes to modified proteins, such as oxLDL, influences their differentiation to macrophages, an in vitro model system using isolated PBMC maintained in culture in the presence of oxLDL was used. Pretreatment of monocytes with oxLDL caused a faster rate of expression of macrophage-specific functions and loss of monocyte-specific functions compared to unmodified LDL. The effect of oxidation of lipid component of LDL by CuSO(4) and its protein component by HOCl, on mo-mϕ differentiation was studied by monitoring the upregulation of macrophage-specific functions, particularly MMP-9. Chloroquine, a lysosomal degradation blocker, significantly reversed the effect mediated by CuSO(4) oxLDL, indicating the involvement of lysosomal degradation products, while no such effect was observed in HOCl oxLDL-treated cells, indicating the existence of a pathway independent of its lysosomal degradation products. Reversal of the effect of oxLDL by NAC and Calphostin C, an inhibitor of PKC, suggested the activation of RO-mediated signaling pathways. Use of inhibitors of signaling pathways showed that CuSO(4) oxLDL upregulated mϕ-specific MMP-9 through p38 MAPK and Akt-dependent pathways, while HOCl oxLDL utilized ERK ½ and Akt. Further analysis showed the activation of PPARγ and AP-1 in CuSO(4) oxLDL, while HOCl-oxLDL-mediated effect involved NFκB and AP-1. These results suggest that lipid oxLDL- and protein oxLDL-mediated upregulation of mo-mϕ-specific functions involve lysosomal degradation-dependent and -independent activation of intracellular signaling pathways.

  9. Integrins mediate mechanical compression–induced endothelium-dependent vasodilation through endothelial nitric oxide pathway

    PubMed Central

    Lu, Xiao

    2015-01-01

    Cardiac and skeletal muscle contraction lead to compression of intramuscular arterioles, which, in turn, leads to their vasodilation (a process that may enhance blood flow during muscle activity). Although endothelium-derived nitric oxide (NO) has been implicated in compression-induced vasodilation, the mechanism whereby arterial compression elicits NO production is unclear. We cannulated isolated swine (n = 39) myocardial (n = 69) and skeletal muscle (n = 60) arteriole segments and exposed them to cyclic transmural pressure generated by either intraluminal or extraluminal pressure pulses to simulate compression in contracting muscle. We found that the vasodilation elicited by internal or external pressure pulses was equivalent; moreover, vasodilation in response to pressure depended on changes in arteriole diameter. Agonist-induced endothelium-dependent and -independent vasodilation was used to verify endothelial and vascular smooth muscle cell viability. Vasodilation in response to cyclic changes in transmural pressure was smaller than that elicited by pharmacological activation of the NO signaling pathway. It was attenuated by inhibition of NO synthase and by mechanical removal of the endothelium. Stemming from previous observations that endothelial integrin is implicated in vasodilation in response to shear stress, we found that function-blocking integrin α5β1 or αvβ3 antibodies attenuated cyclic compression–induced vasodilation and NOx (NO−2 and NO−3) production, as did an RGD peptide that competitively inhibits ligand binding to some integrins. We therefore conclude that integrin plays a role in cyclic compression–induced endothelial NO production and thereby in the vasodilation of small arteries during cyclic transmural pressure loading. PMID:26324675

  10. Fenofibrate suppressed proliferation and migration of human neuroblastoma cells via oxidative stress dependent of TXNIP upregulation

    SciTech Connect

    Su, Cunjin; Shi, Aiming; Cao, Guowen; Tao, Tao; Chen, Ruidong; Hu, Zhanhong; Shen, Zhu; Tao, Hong; Cao, Bin; Hu, Duanmin; Bao, Junjie

    2015-05-15

    There are no appropriate drugs for metastatic neuroblastoma (NB), which is the most common extra-cranial solid tumor for childhood. Thioredoxin binding protein (TXNIP), the endogenous inhibitor of ROS elimination, has been identified as a tumor suppressor in various solid tumors. It reported that fenofibrate exerts anti-tumor effects in several human cancer cell lines. However, its detail mechanisms remain unclear. The present study assessed the effects of fenofibrate on NB cells and investigated TXNIP role in its anti-tumor mechanisms. We used MTT assay to detect cells proliferation, starch wound test to investigate cells migration, H{sub 2}DCF-DA to detect intracellular ROS, siRNA to interfere TXNIP and peroxisome proliferator-androgen receptor-alpha (PPAR-α) expression, western blot to determine protein levels, flow cytometry to analyze apoptosis. Fenofibrate suppressed proliferation and migration of NB cells, remarkably increased intracellular ROS, upregulated TXNIP expression, promoted cell apoptosis. Furthermore, inhibition of TXNIP expression attenuated anti-tumor effects of fenofibrate, while inhibition of PPAR-α had no influences. Our results indicated the anti-tumor role of fenofibrate on NB cells by exacerbating oxidative stress and inducing apoptosis was dependent on the upregulation of TXNIP. - Highlights: • We found that fenofibrate suppressed proliferation and migration of NB cells. • We found that fenofibrate remarkably increased intracellular ROS, upregulated TXNIP expression, and promoted cell apoptosis. • Inhibition of TXNIP expression attenuated anti-tumor effects of fenofibrate, while inhibition of PPAR-α had no influences. • Our results indicated the anti-tumor role of fenofibrate on NB cells was dependent on the upregulation of TXNIP.

  11. Dependence of the critical temperature in overdoped copper oxides on superfluid density

    SciTech Connect

    Božović, I.; He, X.; Wu, J.; Bollinger, A. T.

    2016-08-17

    The physics of underdoped copper-oxide superconductors, including the pseudogap, spin and charge ordering, and their relation to superconductivity1-3, is intensely debated. The overdoped side is perceived as simpler, with strongly-correlated fermion physics evolving smoothly into the conventional Bardeen-Cooper-Schrieffer (BCS) behavior. Pioneering studies on a few overdoped samples4-11 indicated that the superfluid density was much smaller than expected, but this was attributed to pair-breaking, disorder, and phase separation. Here, we test this conjecture by studying how the magnetic penetration depth λ and the phase stiffness ρs depend on temperature and doping, scanning densely the entire overdoped side of the La2-xSrxCuO4 (LSCO) phase diagram. We have measured the absolute values of λ and ρs to the accuracy of ±1% in thousands of cuprate samples; the large statistics reveals clear trends and intrinsic properties. The films are quite homogeneous; variations in the critical temperature (Tc) within a film are very small (< 1 K). At every doping, ρs(T) decreases linearly with temperature. The Tc(ρ s0) dependence is linear but with an offset, (Tc - T0) ∝ ρs0 where T0 ≈ 7 K, except very close to the origin where Tc ∝ √ρ s0. This scaling law defies the standard BCS description, posing a challenge to theory.

  12. Age-Dependent Paraoxonase 1 (PON1) Activity and LDL Oxidation in Wistar Rats during Their Entire Lifespan

    PubMed Central

    Kumar, Dileep

    2014-01-01

    Paraoxonase 1 (PON1) is an HDL bound enzyme which plays a key role in the protection of LDL and HDL from oxidation by hydrolyzing activated phospholipids and lipid peroxide products. Oxidative stress plays a crucial role in the development of atherosclerosis by oxidation of LDL. This study was conducted to determine age-dependent changes in plasma PON1 arylesterase activity and LDL oxidation in rats during their entire lifespan. 48 Wistar strain rats were grouped in six different age groups (1, 4, 8, 12, 18, and 24 months). We observe a significant (P < 0.001) age-dependent decrease in plasma PON1 arylesterase activity correlating with increase in susceptibility of LDL oxidation and increase in plasma MDA level concomitantly with a significant (P < 0.001) decrease in plasma radical scavenging activity after 8 months. The reduction of PON1 and free radical scavenging activity with age could have a considerable impact on the increased incidence of atherosclerosis with age. Our observation of a significant decline in PON1 activity which correlates with increased LDL oxidation after 8 months of age is an interesting observation and needs further investigation. PMID:24971380

  13. Oxidation of the alarmin IL-33 regulates ST2-dependent inflammation

    PubMed Central

    Cohen, E. Suzanne; Scott, Ian C.; Majithiya, Jayesh B.; Rapley, Laura; Kemp, Benjamin P.; England, Elizabeth; Rees, D. Gareth; Overed-Sayer, Catherine L.; Woods, Joanne; Bond, Nicholas J.; Veyssier, Christel Séguy; Embrey, Kevin J.; Sims, Dorothy A.; Snaith, Michael R.; Vousden, Katherine A.; Strain, Martin D.; Chan, Denice T. Y.; Carmen, Sara; Huntington, Catherine E.; Flavell, Liz; Xu, Jianqing; Popovic, Bojana; Brightling, Christopher E.; Vaughan, Tristan J.; Butler, Robin; Lowe, David C.; Higazi, Daniel R.; Corkill, Dominic J.; May, Richard D.; Sleeman, Matthew A.; Mustelin, Tomas

    2015-01-01

    In response to infections and irritants, the respiratory epithelium releases the alarmin interleukin (IL)-33 to elicit a rapid immune response. However, little is known about the regulation of IL-33 following its release. Here we report that the biological activity of IL-33 at its receptor ST2 is rapidly terminated in the extracellular environment by the formation of two disulphide bridges, resulting in an extensive conformational change that disrupts the ST2 binding site. Both reduced (active) and disulphide bonded (inactive) forms of IL-33 can be detected in lung lavage samples from mice challenged with Alternaria extract and in sputum from patients with moderate–severe asthma. We propose that this mechanism for the rapid inactivation of secreted IL-33 constitutes a ‘molecular clock' that limits the range and duration of ST2-dependent immunological responses to airway stimuli. Other IL-1 family members are also susceptible to cysteine oxidation changes that could regulate their activity and systemic exposure through a similar mechanism. PMID:26365875

  14. In Situ Study of Strain-Dependent Ion Conductivity of Stretchable Polyethylene Oxide Electrolyte

    PubMed Central

    Kelly, Taylor; Ghadi, Bahar Moradi; Berg, Sean; Ardebili, Haleh

    2016-01-01

    There is a strong need in developing stretchable batteries that can accommodate stretchable or irregularly shaped applications including medical implants, wearable devices and stretchable electronics. Stretchable solid polymer electrolytes are ideal candidates for creating fully stretchable lithium ion batteries mainly due to their mechanical and electrochemical stability, thin-film manufacturability and enhanced safety. However, the characteristics of ion conductivity of polymer electrolytes during tensile deformation are not well understood. Here, we investigate the effects of tensile strain on the ion conductivity of thin-film polyethylene oxide (PEO) through an in situ study. The results of this investigation demonstrate that both in-plane and through-plane ion conductivities of PEO undergo steady and linear growths with respect to the tensile strain. The coefficients of strain-dependent ion conductivity enhancement (CSDICE) for in-plane and through-plane conduction were found to be 28.5 and 27.2, respectively. Tensile stress-strain curves and polarization light microscopy (PLM) of the polymer electrolyte film reveal critical insights on the microstructural transformation of stretched PEO and the potential consequences on ionic conductivity. PMID:26831948

  15. X-ray absorption spectroscopy of titanium oxide by time dependent density functional calculations.

    PubMed

    Fronzoni, G; De Francesco, R; Stener, M; Causà, M

    2006-05-25

    The potentiality of the time dependent density functional theory (TDDFT) for the description of core excitation spectra (XAS) in transition metal oxides is analyzed, considering the rutile form of TiO(2) as a test case. Cluster models are adopted to mimic the bulk, embedded within an array of point charges to simulate the Madelung potential. All of the edges, titanium and oxygen K and titanium L edges, are considered, and the TDDFT results are compared with the experimental data in order to assess the performance of the theoretical approach in dealing with this complex class of compounds. Satisfactory results have been obtained for the Ti and O K edges, while in the case of the Ti L edge some discrepancies with the experiment are still present. The configuration mixing explicitly included in the TDDFT model strongly influences the distribution of the 2p metal oscillator strength. The origin of the spectral features is investigated with the help of the partial density of the virtual states (PDOS) calculated for each core hole considered, which can be qualitatively compared with the theoretical spectra calculated in the Kohn-Sham one-electron approach.

  16. Mitochondrial dependent oxidative stress in cell culture induced by laser radiation at 1265 nm.

    PubMed

    Saenko, Yury V; Glushchenko, Eugenia S; Zolotovskii, Igor O; Sholokhov, Evgeny; Kurkov, Andrey

    2016-04-01

    Photodynamic therapy is the main technique applied for surface carcinoma treatment. This technique employs singlet oxygen generated via a laser excited photosensitizer as a main damaging agent. However, prolonged sensitivity to intensive light, relatively low tissue penetration by activating light the cost of photosensitizer (PS) administration can limit photodynamic therapy applications. Early was reported singlet oxygen generation without photosensitizer induced by a laser irradiation at the wavelength of 1250-1270 nm. Here, we study the dynamics of oxidative stress, DNA damage, changes of mitochondrial potential, and mitochondrial mass induced by a laser at 1265 nm have been studied in HCT-116 and CHO-K cells. Laser irradiation of HCT-116 and CHO-K cells has induced a dose-dependent cell death via increasing intracellular reactive oxygen species (ROS) concentration, increase of DNA damage, decrease of mitochondrial potential, and reduced glutathione. It has been shown that, along with singlet oxygen generation, the increase of the intracellular ROS concentration induced by mitochondrial damage contributes to the damaging effect of the laser irradiation at 1265 nm.

  17. In Situ Study of Strain-Dependent Ion Conductivity of Stretchable Polyethylene Oxide Electrolyte

    NASA Astrophysics Data System (ADS)

    Kelly, Taylor; Ghadi, Bahar Moradi; Berg, Sean; Ardebili, Haleh

    2016-02-01

    There is a strong need in developing stretchable batteries that can accommodate stretchable or irregularly shaped applications including medical implants, wearable devices and stretchable electronics. Stretchable solid polymer electrolytes are ideal candidates for creating fully stretchable lithium ion batteries mainly due to their mechanical and electrochemical stability, thin-film manufacturability and enhanced safety. However, the characteristics of ion conductivity of polymer electrolytes during tensile deformation are not well understood. Here, we investigate the effects of tensile strain on the ion conductivity of thin-film polyethylene oxide (PEO) through an in situ study. The results of this investigation demonstrate that both in-plane and through-plane ion conductivities of PEO undergo steady and linear growths with respect to the tensile strain. The coefficients of strain-dependent ion conductivity enhancement (CSDICE) for in-plane and through-plane conduction were found to be 28.5 and 27.2, respectively. Tensile stress-strain curves and polarization light microscopy (PLM) of the polymer electrolyte film reveal critical insights on the microstructural transformation of stretched PEO and the potential consequences on ionic conductivity.

  18. Measurements of Location-Dependent Nitric Oxide Levels on Skin Surface in relation to Acupuncture Point.

    PubMed

    Ha, Yejin; Kim, Misun; Nah, Jiseon; Suh, Minah; Lee, Youngmi

    2012-01-01

    Location-dependent skin surface's partial nitric oxide pressure (pNO) is studied using highly sensitive amperometric NO microsensor with a small sensing area (diameter  = 76 μm). The pNO level of LI4 (Hegu) acupuncture point is measured and compared with the pNO level of nonacupuncture point. In addition, the mapping of pNO is carried out over the left wrist skin area one- as well as two-dimensionally. Statistically higher pNO levels near the position of acupuncture points than non-acupuncture points are observed consistently, implying tight relationship between the level of NO release of skin and acupuncture points. The amperometric planar NO microsensor successfully monitors the heterogeneity of skin pNO distribution in high spatial resolution due to its advantageous features such as high sensitivity and small sensing dimension. The current study suggests the direct connection between NO and acupuncture points and possibly provides beneficial information to understand physiological roles and basis of the acupuncture points.

  19. Shape-Dependent Surface Reactivity and Antimicrobial Activity of Nano-Cupric Oxide.

    PubMed

    Gilbertson, Leanne M; Albalghiti, Eva M; Fishman, Zachary S; Perreault, François; Corredor, Charlie; Posner, Jonathan D; Elimelech, Menachem; Pfefferle, Lisa D; Zimmerman, Julie B

    2016-04-05

    Shape of engineered nanomaterials (ENMs) can be used as a design handle to achieve controlled manipulation of physicochemical properties. This tailored material property approach necessitates the establishment of relationships between specific ENM properties that result from such manipulations (e.g., surface area, reactivity, or charge) and the observed trend in behavior, from both a functional performance and hazard perspective. In this study, these structure-property-function (SPF) and structure-property-hazard (SPH) relationships are established for nano-cupric oxide (n-CuO) as a function of shape, including nanospheres and nanosheets. In addition to comparing these shapes at the nanoscale, bulk CuO is studied to compare across length scales. The results from comprehensive material characterization revealed correlations between CuO surface reactivity and bacterial toxicity with CuO nanosheets having the highest surface reactivity, electrochemical activity, and antimicrobial activity. While less active than the nanosheets, CuO nanoparticles (sphere-like shape) demonstrated enhanced reactivity compared to the bulk CuO. This is in agreement with previous studies investigating differences across length-scales. To elucidate the underlying mechanisms of action to further explain the shape-dependent behavior, kinetic models applied to the toxicity data. In addition to revealing different CuO material kinetics, trends in observed response cannot be explained by surface area alone. The compiled results contribute to further elucidate pathways toward controlled design of ENMs.

  20. Oxidants downstream from superoxide inhibit nitric oxide production by vascular endothelium--a key role for selenium-dependent enzymes in vascular health.

    PubMed

    McCarty, M F

    1999-10-01

    Although superoxide can directly quench endothelium-generated nitric oxide (NO), there is considerable evidence that oxidants derived from superoxide--notably peroxides and their further derivatives--can also impair NO bioactivity. In part, this reflects inhibition of NO synthase activity, perhaps mediated by the oxidation of labile sulfhydryl groups, as well as the activation of protein kinase C. Selenium deficiency exacerbates these effects, presumably owing to the crucial role of selenium-dependent thioredoxin reductase and glutathione peroxidases in preventing and reversing oxidant damage to proteins. High-normal homocyst(e)ine levels may induce an 'effective selenium deficiency' by suppressing glutathione peroxidase transcription in endothelial cells. Considerable epidemiology, primarily of European origin, points to mediocre selenium nutrition as a significant vascular risk factor; the risk associated with elevated plasma homocyst(e)ine levels is now well established. In addition to preventing LDL oxidation, vitamin E can be expected to minimize the contribution of lipid peroxides to endothelial dysfunction. Lipoic acid, which can function in vivo as a versatile antioxidant and sulfhydryl reductant, may have particular value for protecting endothelium from oxidants; its clinical utility in diabetic neuropathy may reflect this benefit. Good selenium status, as well as supra-nutritional intakes of lipoic acid, may down-regulate cytokine-mediated endothelial activation by helping to maintain the proper structure of oxidant-labile proteins--such as tyrosine phosphatases--that modulate this signaling. It can be concluded that a number of supplemental nutrients--including selenium, vitamin E, lipoic acid, and the vitamins that promote catabolism of homocysteine--have the potential to promote vascular health by mitigating the adverse impact of superoxide-derived oxidants on endothelial function.

  1. Hippocampal adult neurogenesis is maintained by Neil3-dependent repair of oxidative DNA lesions in neural progenitor cells.

    PubMed

    Regnell, Christine Elisabeth; Hildrestrand, Gunn Annette; Sejersted, Yngve; Medin, Tirill; Moldestad, Olve; Rolseth, Veslemøy; Krokeide, Silje Zandstra; Suganthan, Rajikala; Luna, Luisa; Bjørås, Magnar; Bergersen, Linda H

    2012-09-27

    Accumulation of oxidative DNA damage has been proposed as a potential cause of age-related cognitive decline. The major pathway for removal of oxidative DNA base lesions is base excision repair, which is initiated by DNA glycosylases. In mice, Neil3 is the main DNA glycosylase for repair of hydantoin lesions in single-stranded DNA of neural stem/progenitor cells, promoting neurogenesis. Adult neurogenesis is crucial for maintenance of hippocampus-dependent functions involved in behavior. Herein, behavioral studies reveal learning and memory deficits and reduced anxiety-like behavior in Neil3(-/-) mice. Neural stem/progenitor cells from aged Neil3(-/-) mice show impaired proliferative capacity and reduced DNA repair activity. Furthermore, hippocampal neurons in Neil3(-/-) mice display synaptic irregularities. It appears that Neil3-dependent repair of oxidative DNA damage in neural stem/progenitor cells is required for maintenance of adult neurogenesis to counteract the age-associated deterioration of cognitive performance.

  2. The dependence of room-temperature oxidation of silicon catalyzed by Cu3Si on the silicide grain size

    NASA Astrophysics Data System (ADS)

    Liu, C. S.; Chen, L. J.

    1994-03-01

    The dependence of room-temperature oxidation of silicon catalyzed by Cu3Si on the silicide grain size has been investigated by transmission electron microscopy and x-ray diffractometry. The thickness of the SiO2 layer was found to decrease with the average grain size of the starting Cu3Si layer. High-resolution transmission electron microscopy revealed that oxidation is initiated at the grain boundaries. Oxide film as thick as 4.5 μm, compared to a previous record of about 2 μm, was grown at room temperature over a period of two weeks in (001) samples. The growth of thick oxide films was achieved by minimizing the grain size of Cu3Si through a reaction between Cu and an intermediate amorphous silicon layer at 200 °C.

  3. Oral sapropterin acutely augments reflex vasodilation in aged human skin through nitric oxide-dependent mechanisms.

    PubMed

    Stanhewicz, Anna E; Alexander, Lacy M; Kenney, W Larry

    2013-10-01

    Functional constitutive nitric oxide synthase (NOS) and its cofactor tetrahydrobiopterin (BH4) are required for full reflex cutaneous vasodilation and are attenuated in primary aging. Acute, locally administered BH4 increases reflex vasodilation through NO-dependent mechanisms in aged skin. We hypothesized that oral sapropterin (Kuvan, shelf-stable pharmaceutical formulation of BH4) would augment reflex vasodilation in aged human skin during hyperthermia. Nine healthy human subjects (76 ± 1 yr) ingested sapropterin (10 mg/kg) or placebo in a randomized double-blind crossover design. Venous blood samples were collected prior to, and 3 h following, ingestion of sapropterin for measurement of plasma BH4. Three intradermal microdialysis fibers were placed in the forearm skin for local delivery of 1) lactated Ringer's solution, 2) 10 mM BH4, and 3) 20 mM N(G)-nitro-l-arginine methyl ester (l-NAME) to inhibit NOS. Red cell flux was measured at each site by laser-Doppler flowmetry (LDF) as reflex vasodilation was induced using a water-perfused suit. At 1°C rise in oral temperature, mean body temperature was clamped and 20 mM l-NAME was perfused at each site. Cutaneous vascular conductance was calculated (CVC = LDF/MAP) and expressed as a percentage of maximum (%CVCmax 28 mM sodium nitroprusside and local heat 43°C). Plasma concentrations of BH4 were significantly elevated 3 h after ingestion of sapropterin (0 h: 19.1 ± 2 pmol/ml vs. 3 h: 43.8 ± 3 pmol/ml; P < 0.001). Sapropterin increased NO-dependent vasodilation at control site (placebo: 14 ± 1 %CVCmax vs. sapropterin: 25 ± 4 %CVCmax; P = 0.004). Local BH4 administration increased NO-dependent vasodilation compared with control in placebo trials only (control: 14 ± 1 %CVCmax vs. BH4-treated: 24 ± 3 %CVCmax; P = 0.02). These data suggest oral sapropterin increases bioavailable BH4 in aged skin microvasculature sufficiently to increase NO synthesis through NOS and that sapropterin may be a viable intervention to

  4. Adaptation to Ephemeral Habitat May Overcome Natural Barriers and Severe Habitat Fragmentation in a Fire-Dependent Species, the Bachman's Sparrow (Peucaea aestivalis)

    PubMed Central

    Cerame, Blain; Cox, James A.; Brumfield, Robb T.; Tucker, James W.; Taylor, Sabrina S.

    2014-01-01

    Bachman's Sparrow (Peucaea aestivalis) is a fire-dependent species that has undergone range-wide population declines in recent decades. We examined genetic diversity in Bachman's Sparrows to determine whether natural barriers have led to distinct population units and to assess the effect of anthropogenic habitat loss and fragmentation. Genetic diversity was examined across the geographic range by genotyping 226 individuals at 18 microsatellite loci and sequencing 48 individuals at mitochondrial and nuclear genes. Multiple analyses consistently demonstrated little genetic structure and high levels of genetic variation, suggesting that populations are panmictic. Based on these genetic data, separate management units/subspecies designations or translocations to promote gene flow among fragmented populations do not appear to be necessary. Panmixia in Bachman's Sparrow may be a consequence of an historical range expansion and retraction. Alternatively, high vagility in Bachman's Sparrow may be an adaptation to the ephemeral, fire-mediated habitat that this species prefers. In recent times, high vagility also appears to have offset inbreeding and loss of genetic diversity in highly fragmented habitat. PMID:25180939

  5. Heregulin-HER3-HER2 signaling promotes matrix metalloproteinase-dependent blood-brain-barrier transendothelial migration of human breast cancer cell lines.

    PubMed

    Momeny, Majid; Saunus, Jodi M; Marturana, Flavia; McCart Reed, Amy E; Black, Debra; Sala, Gianluca; Iacobelli, Stefano; Holland, Jane D; Yu, Dihua; Da Silva, Leonard; Simpson, Peter T; Khanna, Kum Kum; Chenevix-Trench, Georgia; Lakhani, Sunil R

    2015-02-28

    HER2-positive breast tumors are associated with a high risk of brain relapse. HER3 is thought to be an indispensible signaling substrate for HER2 (encoded by ERBB2) and is induced in breast cancer-brain metastases, though the molecular mechanisms by which this oncogenic dimer promotes the development of brain metastases are still elusive. We studied the effects of the HER3-HER2 ligand, heregulin (neuregulin-1, broadly expressed in the brain), on luminal breast cancer cell lines in vitro. Treatment of SKBr3 (ERBB2-amplified), MDA-MB-361 (ERBB2-amplified, metastatic brain tumor-derived) and MCF7 (HER2-positive, not ERBB2-amplified) cells with exogenous heregulin increased proliferation and adhesive potential, concomitant with induction of cyclin D1 and ICAM-1, and suppression of p27. All three cell lines invaded through matrigel toward a heregulin chemotactic signal in transwell experiments, associated with activation of extracellular cathepsin B and matrix metalloproteinase-9 (MMP-9). Moreover, heregulin induced breast cancer cell transmigration across a tight barrier of primary human brain microvascular endothelia. This was dependent on the activity of HER2, HER3 and MMPs, and was completely abrogated by combination HER2-HER3 blockade using Herceptin® and the humanized HER3 monoclonal antibody, EV20. Collectively these data suggest mechanisms by which the HER3-HER2 dimer promotes development of metastatic tumors in the heregulin-rich brain microenvironment.

  6. Adaptation to ephemeral habitat may overcome natural barriers and severe habitat fragmentation in a fire-dependent species, the Bachman's Sparrow (Peucaea aestivalis).

    PubMed

    Cerame, Blain; Cox, James A; Brumfield, Robb T; Tucker, James W; Taylor, Sabrina S

    2014-01-01

    Bachman's Sparrow (Peucaea aestivalis) is a fire-dependent species that has undergone range-wide population declines in recent decades. We examined genetic diversity in Bachman's Sparrows to determine whether natural barriers have led to distinct population units and to assess the effect of anthropogenic habitat loss and fragmentation. Genetic diversity was examined across the geographic range by genotyping 226 individuals at 18 microsatellite loci and sequencing 48 individuals at mitochondrial and nuclear genes. Multiple analyses consistently demonstrated little genetic structure and high levels of genetic variation, suggesting that populations are panmictic. Based on these genetic data, separate management units/subspecies designations or translocations to promote gene flow among fragmented populations do not appear to be necessary. Panmixia in Bachman's Sparrow may be a consequence of an historical range expansion and retraction. Alternatively, high vagility in Bachman's Sparrow may be an adaptation to the ephemeral, fire-mediated habitat that this species prefers. In recent times, high vagility also appears to have offset inbreeding and loss of genetic diversity in highly fragmented habitat.

  7. Thermal barrier coating system

    NASA Technical Reports Server (NTRS)

    Stecura, S. (Inventor)

    1985-01-01

    An oxide thermal barrier coating comprises ZrO3-Yb2O3 that is plasma sprayed onto a previously applied bond coating. The zirconia is partially stabilized with about 124 w/o ytterbia to insure cubic, monoclinic, and terragonal phases.

  8. Formation of single domain magnetite by green rust oxidation promoted by microbial anaerobic nitrate-dependent iron oxidation

    NASA Astrophysics Data System (ADS)

    Miot, Jennyfer; Li, Jinhua; Benzerara, Karim; Sougrati, Moulay Tahar; Ona-Nguema, Georges; Bernard, Sylvain; Jumas, Jean-Claude; Guyot, François

    2014-08-01

    Biomineralization of magnetite is a central geomicrobiological process that might have played a primordial role over Earth’s history, possibly leaving traces of life in the geological record or controlling trace metal(loid)s and organic pollutants mobility in modern environments. Magnetite biomineralization has been attributed to two main microbial pathways to date (namely magnetotactic bacteria and dissimilatory iron-reducing bacteria). Here, we uncover a new route of magnetite biomineralization involving the anaerobic nitrate-reducing iron(II) oxidizing bacterium Acidovorax sp. strain BoFeN1. Using transmission electron microscopy, scanning transmission X-ray microscopy, transmission Mössbauer spectroscopy and rock magnetic analyses, this strain is shown to promote the transformation of hydroxychloride green rust in equilibrium with dissolved Fe(II) to (1) periplasmic lepidocrocite (γ-FeOOH) and (2) extracellular magnetite, thus leading to strong redox heterogeneities at the nanometer scale. On the one hand, lepidocrocite was associated with protein moieties and exhibited an anisotropic texture, with the elongated axis parallel to the cell wall. On the other hand, magnetite crystals exhibited grain sizes and magnetic properties consistent with stable single domain particles. By comparison, abiotic controls led to a very slow (4 months vs. 2 days in BoFeN1 cultures) and incomplete oxidation of hydroxychloride green rust towards magnetite. As this abiotic magnetite exhibited the same size and magnetic properties (stable single domain particles) as magnetite produced in BoFeN1 cultures, only the co-occurrence of textured Fe(III)-oxides and magnetite, associated with the persistence of organic carbon molecules, might constitute valuable biosignatures to be looked for in the geological record. Our results furthermore contribute to a more complex picture of Fe redox cycling in the environment, providing an additional process of Fe(II)-bearing phase

  9. Growth phase-dependent roles of Sir2 in oxidative stress resistance and chronological lifespan in yeast.

    PubMed

    Kang, Woo Kyu; Kim, Yeong Hyeock; Kim, Byoung-Soo; Kim, Jeong-Yoon

    2014-08-01

    Silent Information Regulator 2 (Sir2), a conserved NAD(+)-dependent histone deacetylase, has been implicated as one of the key factors in regulating stress response and longevity. Here, we report that the role of Sir2 in oxidative stress resistance and chronological lifespan is dependent on growth phase in yeast. In exponential phase, sir2Δ cells were more resistant to H2O2 stress and had a longer chronological lifespan than wild type. By contrast, in post-diauxic phase, sir2Δ cells were less resistant to H2O2 stress and had a shorter chronological lifespan than wild type cells. Similarly, the expression of antioxidant genes, which are essential to cope with oxidative stress, was regulated by Sir2 in a growth phase-dependent manner. Collectively, our findings highlight the importance of the metabolic state of the cell in determining whether Sir2 can protect against or accelerate cellular aging of yeast.

  10. Vertical barriers with increased sorption capacities

    SciTech Connect

    Bradl, H.B.

    1997-12-31

    Vertical barriers are commonly used for the containment of contaminated areas. Due to the very small permeability of the barrier material which is usually in the order of magnitude of 10-10 m/s or less the advective contaminant transport can be more or less neglected. Nevertheless, there will always be a diffusive contaminant transport through the barrier which is caused by the concentration gradient. Investigations have been made to increase the sorption capacity of the barrier material by adding substances such as organoclays, zeolites, inorganic oxides and fly ashes. The contaminants taken into account where heavy metals (Pb) and for organic contaminants Toluole and Phenantrene. The paper presents results of model calculations and experiments. As a result, barrier materials can be designed {open_quotes}tailor-made{close_quotes} depending on the individual contaminant range of each site (e.g. landfills, gasworks etc.). The parameters relevant for construction such as rheological properties, compressive strength and permeability are not affected by the addition of the sorbents.

  11. Time-dependent diffusion in skeletal muscle with the random permeable barrier model (RPBM): Application to normal controls and chronic exertional compartment syndrome patients

    PubMed Central

    Sigmund, Eric E.; Novikov, Dmitry S.; Sui, Dabang; Ukpebor, Obehi; Baete, Steven; Babb, James S.; Liu, Kecheng; Feiweier, Thorsten; Kwon, Jane; Mcgorty, KellyAnne; Bencardino, Jenny; Fieremans, Els

    2014-01-01

    Purpose To collect diffusion tensor imaging (DTI) at multiple diffusion times Td in skeletal muscle in normal subjects and chronic exertional compartment syndrome (CECS) patients and analyze the data with the random permeable barrier model (RPBM) for biophysical specificity. Materials and Methods Using an IRB-approved HIPAA-compliant protocol, seven patients with clinical suspicion of CECS and eight healthy volunteers underwent DTI of the calf muscle in a Siemens MAGNETOM Verio 3-T scanner at rest and after treadmill exertion at 4 different diffusion times. Radial diffusion values λrad were computed for each of 7 different muscle compartments and analyzed with RPBM to produce estimates of free diffusivity D0, fiber diameter a, and permeability κ. Fiber diameter estimates were compared with measurements from literature autopsy reference for several compartments. Response factors (post/pre-exercise ratios) were computed and compared between normal controls and CECS patients using a mixed-model two-way analysis of variance. Results All subjects and muscle compartments showed nearly time-independent diffusion along and strongly time-dependent diffusion transverse to the muscle fibers. RPBM estimates of fiber diameter correlated well with corresponding autopsy reference. D0 showed significant (p<0.05) increases with exercise for volunteers, and a increased significantly (p<0.05) in volunteers. At the group level, response factors of all three parameters showed trends differentiating controls from CECS patients, with patients showing smaller diameter changes (p=0.07), and larger permeability increases (p=0.07) than controls. Conclusions Time-dependent diffusion measurements combined with appropriate tissue modeling can provide enhanced microstructural specificity for in vivo tissue characterization. In CECS patients, our results suggest that high-pressure interfiber edema elevates free diffusion and restricts exercise-induced fiber dilation. Such specificity may be

  12. Acetaminophen Modulates P-Glycoprotein Functional Expression at the Blood-Brain Barrier by a Constitutive Androstane Receptor–Dependent Mechanism

    PubMed Central

    Thompson, Brandon J.; Sanchez-Covarrubias, Lucy; Zhang, Yifeng; Laracuente, Mei-Li; Vanderah, Todd W.; Ronaldson, Patrick T.; Davis, Thomas P.

    2013-01-01

    Effective pharmacologic treatment of pain with opioids requires that these drugs attain efficacious concentrations in the central nervous system (CNS). A primary determinant of CNS drug permeation is P-glycoprotein (P-gp), an endogenous blood-brain barrier (BBB) efflux transporter that is involved in brain-to-blood transport of opioid analgesics (i.e., morphine). Recently, the nuclear receptor constitutive androstane receptor (CAR) has been identified as a regulator of P-gp functional expression at the BBB. This is critical to pharmacotherapy of pain/inflammation, as patients are often administered acetaminophen (APAP), a CAR-activating ligand, in conjunction with an opioid. Our objective was to investigate, in vivo, the role of CAR in regulation of P-gp at the BBB. Following APAP treatment, P-gp protein expression was increased up to 1.4–1.6-fold in a concentration-dependent manner. Additionally, APAP increased P-gp transport of BODIPY-verapamil in freshly isolated rat brain capillaries. This APAP-induced increase in P-gp expression and activity was attenuated in the presence of CAR pathway inhibitor okadaic acid or transcriptional inhibitor actinomycin D, suggesting P-gp regulation is CAR-dependent. Furthermore, morphine brain accumulation was enhanced by P-gp inhibitors in APAP-treated animals, suggesting P-gp–mediated transport. A warm-water (50°C) tail-flick assay revealed a significant decrease in morphine analgesia in animals treated with morphine 3 or 6 hours after APAP treatment, as compared with animals treated concurrently. Taken together, our data imply that inclusion of APAP in a pain treatment regimen activates CAR at the BBB and increases P-gp functional expression, a clinically significant drug-drug interaction that modulates opioid analgesic efficacy. PMID:24019224

  13. Mechanisms of metal ion-dependent oxidation of human low density lipoprotein.

    PubMed

    Lynch, S M; Frei, B

    1996-04-01

    Although either copper or iron is essential for oxidation of human low density lipoprotein (LDL) by vascular cells, the mechanism is unknown. In our experiments copper- and iron-mediated LDL oxidation was found to proceed by different mechanisms. Oxidation of LDL by iron requires superoxide and proceeds by a hydroxyl radical-independent mechanism involving reduction of iron from the ferric to the ferrous form. In contrast, copper-mediated LDL oxidation involves direct reduction of copper from the cupric to the cuprous form by LDL.

  14. Endothelial Cells Derived from the Blood-Brain Barrier and Islets of Langerhans Differ in their Response to the Effects of Bilirubin on Oxidative Stress Under Hyperglycemic Conditions.

    PubMed

    Kapitulnik, Jaime; Benaim, Clara; Sasson, Shlomo

    2012-01-01

    Unconjugated bilirubin (UCB) is a neurotoxic degradation product of heme. Its toxic effects include induction of apoptosis, and ultimately neuronal cell death. However, at low concentrations, UCB is a potent antioxidant that may protect cells and tissues against oxidative stress by neutralizing toxic metabolites such as reactive oxygen species (ROS). High glucose levels (hyperglycemia) generate reactive metabolites. Endothelial cell dysfunction, an early vascular complication in diabetes, has been associated with hyperglycemia-induced oxidative stress. Both glucose and UCB are substrates for transport proteins in microvascular endothelial cells of the blood-brain barrier (BBB). In the current study we show that UCB (1-40 μM) induces apoptosis and reduces survival of bEnd3 cells, a mouse brain endothelial cell line which serves as an in vitro model of the BBB. These deleterious effects of UCB were enhanced in the presence of high glucose (25 mM) levels. Interestingly, the bEnd3 cells exhibited an increased sensitivity to the apoptotic effects of UCB when compared to the MS1 microcapillary endothelial cell line. MS1 cells originate from murine pancreatic islets of Langerhans, and are devoid of the barrier characteristics of BBB-derived endothelial cells. ROS production was increased in both bEnd3 and MS1 cells exposed to high glucose, as compared with cells exposed to normal (5.5 mM) glucose levels. While UCB (0.1-40 μM) did not alter ROS production in cells exposed to normal glucose, relatively low ("physiological") UCB concentrations (0.1-5 μM) attenuated ROS generation in both cell lines exposed to high glucose levels. Most strikingly, higher UCB concentrations (20-40 μM) increased ROS generation in bEnd3 cells exposed to high glucose, but not in similarly treated MS1 cells. These results may be of critical importance for understanding the vulnerability of the BBB endothelium upon exposure to increasing UCB levels under hyperglycemic conditions.

  15. Diosmectite-zinc oxide composite improves intestinal barrier restoration and modulates TGF-β1, ERK1/2, and Akt in piglets after acetic acid challenge.

    PubMed

    Song, Z-H; Ke, Y-L; Xiao, K; Jiao, L-F; Hong, Q-H; Hu, C-H

    2015-04-01

    The present study evaluated the beneficial effect of diosmectite-zinc oxide composite (DS-ZnO) on improving intestinal barrier restoration in piglets after acetic acid challenge and explored the underlying mechanisms. Twenty-four 35-d-old piglets (Duroc × Landrace × Yorkshire), with an average weight of 8.1 kg, were allocated to 4 treatment groups. On d 1 of the trial, colitis was induced via intrarectal injection of acetic acid (10 mL of 10% acetic acid [ACA] solution for ACA, DS-ZnO, and mixture of diosmectite [DS] and ZnO [DS+ZnO] groups) and the control group was infused with saline. Twenty-four hours after challenged, piglets were fed with the following diets: 1) control group (basal diet), 2) ACA group (basal diet), 3) DS-ZnO group (basal diet supplemented with DS-ZnO), and 4) DS+ZnO group (mixture of 1.5 g diosmectite [DS]/kg and 500 mg Zn/kg from ZnO [equal amount of DS and ZnO in the DS-ZnO treatment group]). On d 8 of the trial, piglets were sacrificed. The results showed that DS-ZnO supplementation improved (P < 0.05) ADG, ADFI, and transepithelial electrical resistance and decreased (P < 0.05) fecal scores, crypt depth, and fluorescein isothiocyanate-dextran 4 kDa (FD4) influx as compared with ACA group. Moreover, DS-ZnO increased (P < 0.05) occludin, claudin-1, and zonula occluden-1 expressions; reduced (P < 0.05) caspase-9 and caspase-3 activity and Bax expression; and improved (P < 0.05) Bcl2, XIAP, and PCNA expression. Diosmectite-zinc oxide composite supplementation also increased (P < 0.05) TGF-β1 expression and ERK1/2 and Akt activation. These results suggest that DS-ZnO attenuates the acetic acid-induced colitis by improving mucosa barrier restoration, inhibiting apoptosis, and improving intestinal epithelial cells proliferation and modulation of TGF-β1 and ERK1/2 and Akt signaling pathway.

  16. Oxidative phosphorylation-dependent regulation of cancer cell apoptosis in response to anticancer agents

    SciTech Connect

    Yadav, N.; Kumar, S.; Marlowe, T.; Chaudhary, A. K.; Kumar, R.; Wang, J.; O'Malley, J.; Boland, P. M.; Jayanthi, S.; Kumar, T. K. S.; Yadava, N.; Chandra, D.

    2015-11-05

    Cancer cells tend to develop resistance to various types of anticancer agents, whether they adopt similar or distinct mechanisms to evade cell death in response to a broad spectrum of cancer therapeutics is not fully defined. Current study concludes that DNA-damaging agents (etoposide and doxorubicin), ER stressor (thapsigargin), and histone deacetylase inhibitor (apicidin) target oxidative phosphorylation (OXPHOS) for apoptosis induction, whereas other anticancer agents including staurosporine, taxol, and sorafenib induce apoptosis in an OXPHOS-independent manner. DNA-damaging agents promoted mitochondrial biogenesis accompanied by increased accumulation of cellular and mitochondrial ROS, mitochondrial protein-folding machinery, and mitochondrial unfolded protein response. Induction of mitochondrial biogenesis occurred in a caspase activation-independent mechanism but was reduced by autophagy inhibition and p53-deficiency. Abrogation of complex-I blocked DNA-damage-induced caspase activation and apoptosis, whereas inhibition of complex-II or a combined deficiency of OXPHOS complexes I, III, IV, and V due to impaired mitochondrial protein synthesis did not modulate caspase activity. Mechanistic analysis revealed that inhibition of caspase activation in response to anticancer agents associates with decreased release of mitochondrial cytochrome c in complex-I-deficient cells compared with wild type (WT) cells. Gross OXPHOS deficiencies promoted increased release of apoptosis-inducing factor from mitochondria compared with WT or complex-I-deficient cells, suggesting that cells harboring defective OXPHOS trigger caspase-dependent as well as caspase-independent apoptosis in response to anticancer agents. Interestingly, DNA-damaging agent doxorubicin showed strong binding to mitochondria, which was disrupted by complex-I-deficiency but not by complex-II-deficiency. Thapsigargin-induced caspase activation was reduced upon abrogation of complex-I or gross OXPHOS deficiency

  17. Oxidative phosphorylation-dependent regulation of cancer cell apoptosis in response to anticancer agents

    DOE PAGES

    Yadav, N.; Kumar, S.; Marlowe, T.; ...

    2015-11-05

    Cancer cells tend to develop resistance to various types of anticancer agents, whether they adopt similar or distinct mechanisms to evade cell death in response to a broad spectrum of cancer therapeutics is not fully defined. Current study concludes that DNA-damaging agents (etoposide and doxorubicin), ER stressor (thapsigargin), and histone deacetylase inhibitor (apicidin) target oxidative phosphorylation (OXPHOS) for apoptosis induction, whereas other anticancer agents including staurosporine, taxol, and sorafenib induce apoptosis in an OXPHOS-independent manner. DNA-damaging agents promoted mitochondrial biogenesis accompanied by increased accumulation of cellular and mitochondrial ROS, mitochondrial protein-folding machinery, and mitochondrial unfolded protein response. Induction of mitochondrialmore » biogenesis occurred in a caspase activation-independent mechanism but was reduced by autophagy inhibition and p53-deficiency. Abrogation of complex-I blocked DNA-damage-induced caspase activation and apoptosis, whereas inhibition of complex-II or a combined deficiency of OXPHOS complexes I, III, IV, and V due to impaired mitochondrial protein synthesis did not modulate caspase activity. Mechanistic analysis revealed that inhibition of caspase activation in response to anticancer agents associates with decreased release of mitochondrial cytochrome c in complex-I-deficient cells compared with wild type (WT) cells. Gross OXPHOS deficiencies promoted increased release of apoptosis-inducing factor from mitochondria compared with WT or complex-I-deficient cells, suggesting that cells harboring defective OXPHOS trigger caspase-dependent as well as caspase-independent apoptosis in response to anticancer agents. Interestingly, DNA-damaging agent doxorubicin showed strong binding to mitochondria, which was disrupted by complex-I-deficiency but not by complex-II-deficiency. Thapsigargin-induced caspase activation was reduced upon abrogation of complex-I or gross OXPHOS

  18. Stoichiometry dependent electron transport and gas sensing properties of indium oxide nanowires.

    PubMed

    Gali, Pradeep; Sapkota, Gopal; Syllaios, A J; Littler, Chris; Philipose, U

    2013-06-07

    The effect of stoichiometry of single crystalline In2O3 nanowires on electrical transport and gas sensing was investigated. The nanowires were synthesized by vapor phase transport and had diameters ranging from 80 to 100 nm and lengths between 10 and 20 μm, with a growth direction of [001]. Transport measurements revealed n-type conduction, attributed to the presence of oxygen vacancies in the crystal lattice. As-grown In2O3 nanowires were shown to have a carrier concentration of ≈5 × 10(17) cm(-3), while nanowires that were annealed in wet O2 showed a reduced carrier concentration of less than 10(16) cm(-3). Temperature dependent conductivity measurements on the as-grown nanowires and analysis of the thermally activated Arrhenius conduction for the temperature range of 77-350 K yielded an activation energy of 0.12 eV. This is explained on the basis of carrier exchange that occurs between the surface states and the bulk of the nanowire, resulting in a depleted surface layer of thickness of the order of the Debye length (LD), estimated to be about 3-4 nm for the as-grown nanowires and about 10 times higher for the more stoichiometric nanowires. Significant changes in the electrical conductance of individual In2O3 nanowires were also observed within several seconds of exposure to NH3 and O2 gas molecules at room temperature, thus demonstrating the potential use of In2O3 nanowires as efficient miniaturized chemical sensors. The sensing mechanism is dominated by the nanowire channel conductance, and a simple energy band diagram is used to explain the change in conductivity when gas molecules adsorbed on the nanowire surface influence its electrical properties. Less stoichiometric nanowires were found to be more sensitive to oxidizing gases while more stoichiometric nanowires showed significantly enhanced response to reducing gases.

  19. Control of the neurovascular coupling by nitric oxide-dependent regulation of astrocytic Ca2+ signaling

    PubMed Central

    Muñoz, Manuel F.; Puebla, Mariela; Figueroa, Xavier F.

    2015-01-01

    Neuronal activity must be tightly coordinated with blood flow to keep proper brain function, which is achieved by a mechanism known as neurovascular coupling. Then, an increase in synaptic activity leads to a dilation of local parenchymal arterioles that matches the enhanced metabolic demand. Neurovascular coupling is orchestrated by astrocytes. These glial cells are located between neurons and the microvasculature, with the astrocytic endfeet ensheathing the vessels, which allows fine intercellular communication. The neurotransmitters released during neuronal activity reach astrocytic receptors and trigger a Ca2+ signaling that propagates to the endfeet, activating the release of vasoactive factors and arteriolar dilation. The astrocyte Ca2+ signaling is coordinated by gap junction channels and hemichannels formed by connexins (Cx43 and Cx30) and channels formed by pannexins (Panx-1). The neuronal activity-initiated Ca2+ waves are propagated among neighboring astrocytes directly via gap junctions or through ATP release via connexin hemichannels or pannexin channels. In addition, Ca2+ entry via connexin hemichannels or pannexin channels may participate in the regulation of the astrocyte signaling-mediated neurovascular coupling. Interestingly, nitric oxide (NO) can activate connexin hemichannel by S-nitrosylation and the Ca2+-dependent NO-synthesizing enzymes endothelial NO synthase (eNOS) and neuronal NOS (nNOS) are expressed in astrocytes. Therefore, the astrocytic Ca2+ signaling triggered in neurovascular coupling may activate NO production, which, in turn, may lead to Ca2+ influx through hemichannel activation. Furthermore, NO release from the hemichannels located at astrocytic endfeet may contribute to the vasodilation of parenchymal arterioles. In this review, we discuss the mechanisms involved in the regulation of the astrocytic Ca2+ signaling that mediates neurovascular coupling, with a special emphasis in the possible participation of NO in this process

  20. Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II)-oxidizer

    PubMed Central

    Miot, Jennyfer; Remusat, Laurent; Duprat, Elodie; Gonzalez, Adriana; Pont, Sylvain; Poinsot, Mélanie

    2015-01-01

    Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is, however, thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had, however, never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II) oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate) encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidence of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasmic encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a survival strategy in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern environmental samples. PMID

  1. Hypoxia inducible factor signaling modulates susceptibility to mycobacterial infection via a nitric oxide dependent mechanism.

    PubMed

    Elks, Philip M; Brizee, Sabrina; van der Vaart, Michiel; Walmsley, Sarah R; van Eeden, Fredericus J; Renshaw, Stephen A; Meijer, Annemarie H

    2013-01-01

    Tuberculosis is a current major world-health problem, exacerbated by the causative pathogen, Mycobacterium tuberculosis (Mtb), becoming increasingly resistant to conventional antibiotic treatment. Mtb is able to counteract the bactericidal mechanisms of leukocytes to survive intracellularly and develop a niche permissive for proliferation and dissemination. Understanding of the pathogenesis of mycobacterial infections such as tuberculosis (TB) remains limited, especially for early infection and for reactivation of latent infection. Signaling via hypoxia inducible factor α (HIF-α) transcription factors has previously been implicated in leukocyte activation and host defence. We have previously shown that hypoxic signaling via stabilization of Hif-1α prolongs the functionality of leukocytes in the innate immune response to injury. We sought to manipulate Hif-α signaling in a well-established Mycobacterium marinum (Mm) zebrafish model of TB to investigate effects on the host's ability to combat mycobacterial infection. Stabilization of host Hif-1α, both pharmacologically and genetically, at early stages of Mm infection was able to reduce the bacterial burden of infected larvae. Increasing Hif-1α signaling enhanced levels of reactive nitrogen species (RNS) in neutrophils prior to infection and was able to reduce larval mycobacterial burden. Conversely, decreasing Hif-2α signaling enhanced RNS levels and reduced bacterial burden, demonstrating that Hif-1α and Hif-2α have opposing effects on host susceptibility to mycobacterial infection. The antimicrobial effect of Hif-1α stabilization, and Hif-2α reduction, were demonstrated to be dependent on inducible nitric oxide synthase (iNOS) signaling at early stages of infection. Our findings indicate that induction of leukocyte iNOS by stabilizing Hif-1α, or reducing Hif-2α, aids the host during early stages of Mm infection. Stabilization of Hif-1α therefore represents a potential target for therapeutic

  2. Oxidative phosphorylation-dependent regulation of cancer cell apoptosis in response to anticancer agents

    PubMed Central

    Yadav, N; Kumar, S; Marlowe, T; Chaudhary, A K; Kumar, R; Wang, J; O'Malley, J; Boland, P M; Jayanthi, S; Kumar, T K S; Yadava, N; Chandra, D

    2015-01-01

    Cancer cells tend to develop resistance to various types of anticancer agents, whether they adopt similar or distinct mechanisms to evade cell death in response to a broad spectrum of cancer therapeutics is not fully defined. Current study concludes that DNA-damaging agents (etoposide and doxorubicin), ER stressor (thapsigargin), and histone deacetylase inhibitor (apicidin) target oxidative phosphorylation (OXPHOS) for apoptosis induction, whereas other anticancer agents including staurosporine, taxol, and sorafenib induce apoptosis in an OXPHOS-independent manner. DNA-damaging agents promoted mitochondrial biogenesis accompanied by increased accumulation of cellular and mitochondrial ROS, mitochondrial protein-folding machinery, and mitochondrial unfolded protein response. Induction of mitochondrial biogenesis occurred in a caspase activation-independent mechanism but was reduced by autophagy inhibition and p53-deficiency. Abrogation of complex-I blocked DNA-damage-induced caspase activation and apoptosis, whereas inhibition of complex-II or a combined deficiency of OXPHOS complexes I, III, IV, and V due to impaired mitochondrial protein synthesis did not modulate caspase activity. Mechanistic analysis revealed that inhibition of caspase activation in response to anticancer agents associates with decreased release of mitochondrial cytochrome c in complex-I-deficient cells compared with wild type (WT) cells. Gross OXPHOS deficiencies promoted increased release of apoptosis-inducing factor from mitochondria compared with WT or complex-I-deficient cells, suggesting that cells harboring defective OXPHOS trigger caspase-dependent as well as caspase-independent apoptosis in response to anticancer agents. Interestingly, DNA-damaging agent doxorubicin showed strong binding to mitochondria, which was disrupted by complex-I-deficiency but not by complex-II-deficiency. Thapsigargin-induced caspase activation was reduced upon abrogation of complex-I or gross OXPHOS deficiency

  3. Control of the neurovascular coupling by nitric oxide-dependent regulation of astrocytic Ca(2+) signaling.

    PubMed

    Muñoz, Manuel F; Puebla, Mariela; Figueroa, Xavier F

    2015-01-01

    Neuronal activity must be tightly coordinated with blood flow to keep proper brain function, which is achieved by a mechanism known as neurovascular coupling. Then, an increase in synaptic activity leads to a dilation of local parenchymal arterioles that matches the enhanced metabolic demand. Neurovascular coupling is orchestrated by astrocytes. These glial cells are located between neurons and the microvasculature, with the astrocytic endfeet ensheathing the vessels, which allows fine intercellular communication. The neurotransmitters released during neuronal activity reach astrocytic receptors and trigger a Ca(2+) signaling that propagates to the endfeet, activating the release of vasoactive factors and arteriolar dilation. The astrocyte Ca(2+) signaling is coordinated by gap junction channels and hemichannels formed by connexins (Cx43 and Cx30) and channels formed by pannexins (Panx-1). The neuronal activity-initiated Ca(2+) waves are propagated among neighboring astrocytes directly via gap junctions or through ATP release via connexin hemichannels or pannexin channels. In addition, Ca(2+) entry via connexin hemichannels or pannexin channels may participate in the regulation of the astrocyte signaling-mediated neurovascular coupling. Interestingly, nitric oxide (NO) can activate connexin hemichannel by S-nitrosylation and the Ca(2+)-dependent NO-synthesizing enzymes endothelial NO synthase (eNOS) and neuronal NOS (nNOS) are expressed in astrocytes. Therefore, the astrocytic Ca(2+) signaling triggered in neurovascular coupling may activate NO production, which, in turn, may lead to Ca(2+) influx through hemichannel activation. Furthermore, NO release from the hemichannels located at astrocytic endfeet may contribute to the vasodilation of parenchymal arterioles. In this review, we discuss the mechanisms involved in the regulation of the astrocytic Ca(2+) signaling that mediates neurovascular coupling, with a special emphasis in the possible participation of NO in

  4. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Ma, Qingxin

    2008-04-03

    The experimental determination of rate constants for atmospheric reactions and how these rate constants vary with temperature remain a crucially important part of atmosphere science. In this study, the temperature dependence of the heterogeneous reaction of carbonyl sulfide (COS) on magnesium oxide (MgO) has been investigated using a Knudsen cell reactor and a temperature-programmed reaction apparatus. We found that the adsorption and the heterogeneous reaction are sensitive to temperature. The initial uptake coefficients (gammat(Ini)) of COS on MgO decrease from 1.07 +/- 0.71 x 10-6 to 4.84 +/- 0.60 x 10-7 with the increasing of temperature from 228 to 300 K, and the steady state uptake coefficients (gammat(SS)) increase from 5.31 +/- 0.06 x 10-8 to 1.68 +/- 0.41 x 10-7 with the increasing of temperature from 240 to 300 K. The desorption rate constants (kdes) were also found to increase slightly with the enhancement of temperature. The empirical formula between the uptake coefficients, desorption rate constants and temperature described in the form of Arrhenius expression were obtained. The activation energies for the heterogeneous reaction and desorption of COS on MgO were measured to be 11.02 +/- 0.34 kJ.mol-1 and 6.30 +/- 0.81 kJ.mol-1, respectively. The results demonstrate that the initial uptake of COS on MgO is mainly contributed by an adsorption process and the steady state uptake is due to a catalytic reaction. The environmental implication was also discussed.

  5. Superoxide-dependent consumption of nitric oxide in biological media may confound in vitro experiments.

    PubMed

    Keynes, Robert G; Griffiths, Charmaine; Garthwaite, John

    2003-01-15

    NO functions ubiquitously as a biological messenger but has also been implicated in various pathologies, a role supported by many reports that exogenous or endogenous NO can kill cells in tissue culture. In the course of experiments aimed at examining the toxicity of exogenous NO towards cultured cells, we found that most of the NO delivered using a NONOate (diazeniumdiolate) donor was removed by reaction with the tissue-culture medium. Two NO-consuming ingredients were identified: Hepes buffer and, under laboratory lighting, the vitamin riboflavin. In each case, the loss of NO was reversed by the addition of superoxide dismutase. The effect of Hepes was observed over a range of NONOate concentrations (producing up to 1 microM NO). Furthermore, from measurements of soluble guanylate cyclase activity, Hepes-dependent NO consumption remained significant at the low nanomolar NO concentrations relevant to physiological NO signalling. The combination of Hepes and riboflavin (in the light) acted synergistically to the extent that, instead of a steady-state concentration of about 1 microM being generated, NO was undetectable (<10 nM). Again, the consumption could be inhibited by superoxide dismutase. A scheme is proposed whereby a "vicious cycle" of superoxide radical (O(2)(.-)) formation occurs as a result of oxidation of Hepes to its radical species, fuelled by the subsequent reaction of O(2)(.-) with NO to form peroxynitrite (ONOO(-)). The inadvertent production of ONOO(-) and other reactive species in biological media, or the associated loss of NO, may contribute to the adverse effects, or otherwise, of NO in vitro.

  6. Nitric oxide-mediated apoptosis of neutrophils through caspase-8 and caspase-3-dependent mechanism

    PubMed Central

    Dubey, Megha; Nagarkoti, Sheela; Awasthi, Deepika; Singh, Abhishek K; Chandra, Tulika; Kumaravelu, J; Barthwal, Manoj K; Dikshit, Madhu

    2016-01-01

    Neutrophils play an indispensable role in killing of invading pathogens by enhancing reactive oxygen species (ROS) and NO generation, and subsequently undergoing apoptosis. Unlike ROS/NOX2, role of NO/NOS still remains undefined in the apoptosis of neutrophils (PMNs) and the present study attempts to decipher the importance of NO/NOS in the neutrophil apoptosis. Prolonged treatment of human PMNs or mice bone marrow derived neutrophils (BMDN) with NO led to enhanced ROS generation, caspase-8/caspase-3 cleavage, reduced mitochondrial membrane potential and finally cellular apoptosis. NO-induced ROS generation led to caspase-8 deglutathionylation and activation, which subsequently activated mitochondrial death pathway via BID (Bcl-2 family protein) cleavage. NO-mediated augmentation of caspase-8 and BID cleavage was significantly prevented in BMDN from neutrophil cytosolic factor-1 (NCF-1) knockout (KO) mice, implying the involvement of NOX2 in NO-induced apoptosis of PMNs. Furthermore, ROS, NO generation and inducible nitric oxide synthase (iNOS) expression were enhanced in a time-dependent manner in human PMNs and mice BMDN undergoing spontaneous apoptosis. Pharmacological and genetic ablation of iNOS in human PMNs and mice BMDN significantly reduced the levels of apoptosis. Impaired apoptosis of BMDN from iNOS KO mice was due to reduced caspase-8 activity which subsequently prevented caspase-3 and -9 activation. Altogether, our results suggest a crucial role of NO/iNOS in neutrophil apoptosis via enhanced ROS generation and caspase-8 mediated activation of mitochondrial death pathway. PMID:27584786

  7. Sediment nitrite-dependent methane-oxidizing microorganisms temporally and spatially shift in the Dongjiang River.

    PubMed

    Long, Yan; Jiang, Xianjin; Guo, Qingwei; Li, Bingxin; Xie, Shuguang

    2017-01-01

    Nitrite-dependent anaerobic methane oxidation (n-damo) process can play an important role in the methane mitigation in the environment. However, the distribution of n-damo organisms in freshwater sediment ecosystem and the associated environmental factors remain essentially unclear. The present study investigated the temporal and spatial dynamics of sediment n-damo community in the freshwater Dongjiang River using quantitative PCR assay and clone library analysis targeting n-damo pmoA gene. Sediment samples were collected at nine locations along the Dongjiang River in May and August in 2015. The remarkable temporal and spatial changes of sediment n-damo community abundance, richness, diversity, and structure occurred in the Dongjiang River and its tributaries. The n-damo pmoA gene in sediments of the Dongjiang River and its tributaries varied from 9.07 × 10(4) to 3.02 × 10(6) copies per gram dry sediment. Compared to the stem of the Dongjiang River, tributaries had relatively higher sediment n-damo community size. Sediment n-damo community abundance was higher in August than in May, while an opposite trend was observed for n-damo community richness and diversity. Sediment n-damo community structure showed a great difference between in May and August. Sediment nitrite nitrogen content was positively correlated to n-damo community abundance, but negatively to richness and diversity. Ammonia nitrogen content showed a positive correlation to n-damo community abundance, while n-damo community diversity was negatively correlated to the ratio of total organic carbon to total nitrogen (C/N). In addition, nitrite nitrogen as well as C/N might influence n-damo community structure.

  8. Thickness dependence of transport properties of doped polycrystalline tin oxide films

    SciTech Connect

    Belanger, D.; Dickson, J.I.; Dodelet, J.P.; Lombos, B.A.

    1985-06-01

    Tin oxide films were deposited by chemical vapor deposition on borosilicate and fused silica substrates using dibutyltin diacetate (DBTD) as tin feedstock and SbC/sub 5/ or CC/sub 3/-CF/sub 3/ as dopants. The film growth rate was measured as a function of dopant/DBTD ratio, temperature, and film thickness. Scanning electron microscopy and x-ray diffraction spectra of the films were used to determine the grain sizes and the preferential orientations of the crystallites in the film as a function of film thickness. Optical and electrical properties were measured. A model is proposed to elucidate the variation of transport properties of doped SnO/sub 2/ as a function of film thickness. It could b shown with this model that the thickness dependence of the conductivity of doped SnO/sub 2/:Sb and SnO/sub 2/:F films could be analyzed in terms of carrier concentration taking into consideration deep-level compensation. The number of carriers is decreased by electron trapping at Sb(III) or Sn(II) surface states when antimony or fluorine are used as dopant, respectively. The model based on results of the literature related to a single crystal with (110) orientation is extended in this work to other crystallite orientations. The present analysis indicates that deep levels appear only on the grain boundary surfaces with (110), (211), and (301) orientations, and not on the (200) and (400) ones. The concentration of free carriers can be calculated on the basis of x-ray diffraction spectra indicating an estimate of the relative fraction of the crystallites with each orientation as a function of the film thickness. The conductivities of the films can be computed using this model and taking a single value for the electron mobility of 19 cm/sup 2/ (V-s)/sup -1/ for all film thickness and a total donor concentration of 2 x 10/sup 20/ cm/sup -3/. All the obtained experimental data can be accounted for exclusively on the basis of film-thickness dependent carrier concentration.

  9. Temperature and voltage dependence of barrier height and ideality factor in Au/0.07 graphene-doped PVA/n-Si structures

    NASA Astrophysics Data System (ADS)

    Altındal Yerişkin, S.; Balbaşı, M.; Demirezen, S.

    2017-01-01

    In this study, Au/0.07 graphene-doped PVA/n-Si structures were fabricated and current conduction mechanism in these structures were investigated in the temperature range of 80-380 K through forward bias current-voltage (I-V) measurements. Main electrical parameters were extracted from I-V data. Zero-bias barrier height (overline{Φ}_{B0} ) and ideality factor (n) were found strong functions of temperature and their values ranged from 0.234 eV and 4.98 (at 80 K) to 0.882 eV and 1.15 (at 380 K), respectively. Φ ap versus q/2kT plot was drawn to obtain an evidence of a Gaussian distribution of the barrier heights (BHs) and it revealed two distinct linear regions with different slopes and intercepts. The mean values of BH (Φ Bo) and zero-bias standard deviation (σ s ) were obtained from the intercept and slope of the linear regions of this plot as 1.30 eV and 0.16 V for the first region (280-380 K) and 0.74 eV and 0.085 V for the second region (80-240 K), respectively. Thus, the values of overline{Φ}_{B0} and effective Richardson constant (A*) were also found from the intercept and slope of the modified Richardson plot [ln(I s /T 2) - q 2 σ {/o 2} /2k 2 T 2 vs q/kT] as 1.31 eV and 130 A/cm2 K2 for the first region and 0.76 eV and 922 A/cm2 K2 for the second region, respectively. The value of A* for the first region was very close to the theoretical value for n-Si (112 A/cm2 K2). The energy density distribution profile of surface states (Nss) was also extracted from the forward bias I-V data by taking into account voltage dependent effective BH (Φe) and n.

  10. Temperature and voltage dependence of barrier height and ideality factor in Au/0.07 graphene-doped PVA/n-Si structures

    NASA Astrophysics Data System (ADS)

    Altındal Yerişkin, S.; Balbaşı, M.; Demirezen, S.

    2017-04-01

    In this study, Au/0.07 graphene-doped PVA/n-Si structures were fabricated and current conduction mechanism in these structures were investigated in the temperature range of 80-380 K through forward bias current-voltage ( I- V) measurements. Main electrical parameters were extracted from I-V data. Zero-bias barrier height (\\overline{Φ}_{B0}) and ideality factor (n) were found strong functions of temperature and their values ranged from 0.234 eV and 4.98 (at 80 K) to 0.882 eV and 1.15 (at 380 K), respectively. Φ ap versus q/2k T plot was drawn to obtain an evidence of a Gaussian distribution of the barrier heights (BHs) and it revealed two distinct linear regions with different slopes and intercepts. The mean values of BH ( Φ Bo) and zero-bias standard deviation (σ s ) were obtained from the intercept and slope of the linear regions of this plot as 1.30 eV and 0.16 V for the first region (280-380 K) and 0.74 eV and 0.085 V for the second region (80-240 K), respectively. Thus, the values of \\overline{Φ}_{B0} and effective Richardson constant ( A*) were also found from the intercept and slope of the modified Richardson plot [ln( I s /T 2) - q 2 σ o 2 /2k 2 T 2 vs q/ kT] as 1.31 eV and 130 A/cm2 K2 for the first region and 0.76 eV and 922 A/cm2 K2 for the second region, respectively. The value of A* for the first region was very close to the theoretical value for n-Si (112 A/cm2 K2). The energy density distribution profile of surface states (Nss) was also extracted from the forward bias I-V data by taking into account voltage dependent effective BH (Φe) and n.

  11. Analysis of temperature dependent current-conduction mechanisms in Au/TiO2/n-4H-SiC (metal/insulator/semiconductor) type Schottky barrier diodes

    NASA Astrophysics Data System (ADS)

    Alialy, S.; Altındal, Ş.; Tanrıkulu, E. E.; Yıldız, D. E.

    2014-08-01

    In order to determine the effective current-conduction mechanisms in Au/TiO2/n-4H-SiC (metal-insulator semiconductor) type Schottky barrier diodes (SBDs), their current-voltage (I-V) measurements were carried out in the temperature range of 200-380 K. Some electrical parameters, such as ideality factor (n), zero-bias barrier height (BH) (ΦBo), series and shunt resistances (Rs, Rsh), were obtained as 5.09, 0.81 eV, 37.43 Ω, and 435 kΩ at 200 K and 2.68, 0.95 eV, 5.99 Ω, and 73 kΩ at 380 K, respectively. The energy density distribution profile of surface states (Nss) was extracted from the forward-bias I-V data by taking into account voltage dependent of the ideality factor (nV), effective BH (Φe), and Rs for 200, 300, and 380 K. The Ln(I) vs V plots are completely parallel in the intermediate bias voltages, which may be well explained by field emission (FE) mechanism for each temperature. On the other hand, the high value of n cannot be explained with this mechanism. Therefore, to explain the change in BH and n with temperature, ΦBo vs q/2kT plot was drawn to obtain an evidence of a Gaussian distribution (GD) of the BHs and thus the mean value of BH (Φ¯Bo) and standard deviation (σso) values were found from this plot as 1.396 eV and 0.176 V, respectively. The Φ¯Bo and Richardson constant (A*) values were found as 1.393 eV and 145.5 A.cm-2 K-2 using modified Ln(Io/T2)-(q2σs2/2k2T2) vs q/kT plot, respectively. It is clear that all of the obtained main electrical parameters were found as a strong function of temperature. These results indicated that the current conduction mechanism in Au/TiO2/n-4 H-SiC (SBD) well obey the FE and GD mechanism rather than other mechanisms.

  12. Age dependent nitro-oxidative load and melatonin receptor expression in the spleen and immunity of goat Capra hircus.

    PubMed

    Singh, Amaresh Kumar; Haldar, Chandana

    2014-12-01

    The decline in the plasma level of melatonin has been associated with increased oxidative stress in the physiological system while aging. The increased levels of oxidants are known to augment the nitro-oxidative stress, which induces the apoptotic factors in lymphoid organs leading to age dependent immunosenescence. There are no reports to date that can suggest how the age dependent nitro-oxidative stress can influence the melatonin membrane MT1/MT2R expression and immune status of any small ruminant. In the present study, we noted the expression of melatonin receptors MT1R and MT2R and inducible nitric oxide synthase (iNOS) along with the apoptotic markers (viz. Bcl-2, Bax and Pro-caspase-3) in the spleen of young, middle-aged and old-aged Indian goat Capra hircus. The lymphocyte proliferation was also recorded along with the total nitrite and nitrate ion concentration (NOx) in the spleen and plasma. An age dependent decline in MT1R and MT2R expressions and lymphocyte proliferation with increased level of reactive nitrogen species (RNS) and iNOS expression was noted. An increased Bax/Bcl-2 ratio and a decreased Pro-caspase-3 expression were observed in the spleen of goat with an age dependent decline in the peripheral melatonin level. This decline in melatonin along with reduced melatonin receptor (MT1/MT2) expression and elevated RNS level in the spleen with aging might have an important role in the regulation of immune function of goats. Our observations suggest that the age-associated immunosenescence observed in goats can be a consequence of declining melatonin and its receptor expression and induction of apoptotic factors influenced by the increased RNS level that deteriorates the proper functioning of the spleen.

  13. NRF2 Oxidative Stress Induced by Heavy Metals is Cell Type Dependent

    EPA Science Inventory

    Exposure to metallic environmental toxicants has been demonstrated to induce a variety of oxidative stress responses in mammalian cells. The transcription factor Nrf2 is activated in response to oxidative stress and coordinates the expression of antioxidant gene products. In this...

  14. Anaerobic, nitrate-dependent oxidation of pyrite nanoparticles by Thiobacillus denitrificans.

    PubMed

    Bosch, Julian; Lee, Keun-Young; Jordan, Guntram; Kim, Kyoung-Woong; Meckenstock, Rainer U

    2012-02-21

    Pyrite is a key mineral in the global biogeochemical cycles of sulfur and iron, yet its anaerobic microbial oxidation has eluded geochemists and microbiologists for decades. Recent reports indicated that anaerobic oxidation of pyrite is occurring, but the mechanism remains unclear. Here, we provide evidence for the capability of Thiobacillus denitrificans to anaerobically oxidize a putatively nanosized pyrite particle fraction with nitrate as electron acceptor. Nanosized pyrite was readily oxidized to ferric iron and sulfate with a rate of 10.1 μM h(-1). The mass balance of pyrite oxidation and nitrate reduction revealed a closed recovery of the electrons. This substantiates a further "missing lithotrophy" in the global cycles of sulfur and iron and emphasizes the high reactivity of nanominerals in the environment.

  15. Inhibition of brain oxidative stress and inducible nitric oxide synthase expression by thymoquinone attenuates the development of morphine tolerance and dependence in mice.

    PubMed

    Abdel-Zaher, Ahmed O; Mostafa, Mostafa G; Farghly, Hanan M; Hamdy, Mostafa M; Omran, Ghada A; Al-Shaibani, Najlaà K M

    2013-02-28

    In this study, the effect of thymoquinone on morphine-induced tolerance and dependence in mice was investigated. Repeated administration of thymoquinone along with morphine attenuated the development of morphine tolerance, as measured by the hot plate test, and dependence, as assessed by naloxone-precipitated withdrawal manifestations. Concurrently, morphine-induced progressive increase in brain malondialdehyde (MDA) level and nitric oxide (NO) production as well as progressive decrease in brain intracellular reduced glutathione (GSH) level and glutathione peroxidase (GSH-Px) activity were inhibited by co-administration of thymoquinone. Morphine-induced progressive increase in brain glutamate level was not inhibited by concomitant administration of thymoquinone. Similarly, co-administration of thymoquinone inhibited naloxone-induced increase in brain MDA level, NO overproduction and decrease in brain intracellular GSH level and GSH-Px activities but it did not inhibit naloxone-induced elevation of brain glutamate level in morphine-dependent mice. The inhibitory effect of thymoquinone on morphine-induced tolerance and dependence on naloxone-induced biochemical alterations in morphine-dependent mice was enhanced by concurrent i.p. administration of the NMDA receptor antagonist, dizocilpine, the antioxidant, N-acetylcysteine or the NO synthase inhibitor, L-N (G)-nitroarginine methyl ester. On the other hand, this inhibitory effect of thymoquinone was antagonized by concurrent i.p. administration of NO precursor, L-arginine. In addition, concomitant administration of thymoquinone inhibited morphine tolerance and dependence-induced increase in inducible but not in neuronal NO synthase mRNA expression in mice brain. These results demonstrate that inhibition of morphine-induced oxidative stress, increase in the expression of brain inducible NO synthase and NO overproduction by thymoquinone can attenuate the development of morphine tolerance and dependence.

  16. Elucidation of barrier homogeneity in ZnO/P3HT:PCBM junctions through temperature dependent I-V characteristics

    NASA Astrophysics Data System (ADS)

    Khare, Neeraj; Zubair Ansari, Mohd; Hoye, Robert L. Z.; Iza, Diana C.; MacManus-Driscoll, Judith L.

    2016-07-01

    The current-voltage (I-V) characteristics of ZnO/P3HT:PCBM junctions using as-deposited ZnO and 300 °C-annealed ZnO (prior to device fabrication) were probed as a function of temperature. The ZnO films were synthesized using two scalable, low temperature methods: Atmospheric pressure spatial atomic layer deposition (AP-SALD) and electrodeposition (ED). In both cases the zero bias Schottky barrier height ({Φ\\text{B}} ) decreases and ideality factor (n) increases with a reduction in the operating temperature of the junctions. This was attributed to the presence of barrier inhomogeneities at the interface from surface states/defects in the ZnO causing a localized variation of work function. For the as-deposited ZnO junctions, two mean barrier heights, arising from a large density of surface states was observed. For the annealed ZnO junction one mean barrier height was observed, indicating reduction in the inhomogeneities of barrier height at the interface for the annealed ZnO. The photoresponce of ZnO/P3HT:PCBM junction was higher for the annealed ZnO which is due to the higher mean barrier height and lower value of ideality factor. This demonstrates that moderate annealing of chemically grown ZnO is crucial for reducing surface defects and barrier inhomogeneities.

  17. Analysis of temperature-dependant current-voltage characteristics and extraction of series resistance in Pd/ZnO Schottky barrier diodes

    NASA Astrophysics Data System (ADS)

    Mayimele, M. A.; van Rensburg, J. P. Janse; Auret, F. D.; Diale, M.

    2016-01-01

    We report on the analysis of current voltage (I-V) measurements performed on Pd/ZnO Schottky barrier diodes (SBDs) in the 80-320 K temperature range. Assuming thermionic emission (TE) theory, the forward bias I-V characteristics were analysed to extract Pd/ZnO Schottky diode parameters. Comparing Cheung's method in the extraction of the series resistance with Ohm's law, it was observed that at lower temperatures (T<180 K) the series resistance decreased with increasing temperature, the absolute minimum was reached near 180 K and increases linearly with temperature at high temperatures (T>200 K). The barrier height and the ideality factor decreased and increased, respectively, with decrease in temperature, attributed to the existence of barrier height inhomogeneity. Such inhomogeneity was explained based on TE with the assumption of Gaussian distribution of barrier heights with a mean barrier height of 0.99 eV and a standard deviation of 0.02 eV. A mean barrier height of 0.11 eV and Richardson constant value of 37 A cm-2 K-2 were determined from the modified Richardson plot that considers the Gaussian distribution of barrier heights.

  18. Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber

    NASA Astrophysics Data System (ADS)

    Chen, Chong; Zhai, Yong; Li, Chunxi; Li, Fumin

    2014-11-01

    Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte.

  19. Magnetic field enhanced convective diffusion of iron oxide nanoparticles in an osmotically disrupted cell culture model of the blood–brain barrier

    PubMed Central

    Sun, Zhizhi; Worden, Matthew; Wroczynskyj, Yaroslav; Yathindranath, Vinith; van Lierop, Johan; Hegmann, Torsten; Miller, Donald W

    2014-01-01

    Purpose The present study examines the use of an external magnetic field in combination with the disruption of tight junctions to enhance the permeability of iron oxide nano