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Sample records for barrier oxidation dependence

  1. Alloy-grain-size dependence of the effectiveness of silica coatings as oxidation barriers on stainless steel

    SciTech Connect

    McDowell, C.S.; Basu, S.N.

    1995-04-01

    In order to determine the effect of alloy grain size on the oxidation properties of silica-coated austenitic Fe-18Cr-20Ni stainless steel, both coarse-grain (100-{mu}m grain size) forms of the alloy were produced. A 1-{mu}m-thick vitreous silica coating was deposited by chemical-vapor deposition on the alloys, which were subjected to isothermal and cyclic oxidation in air at 900{degrees}C. The coarse-grain alloys underwent widespread oxidation below the silica coating, leading to extensive coating spallation. This was attributed to the inability of the alloy to supply a sufficient outward flux of chromium to prevent oxygen penetration through microcracks in the silica coating. Due to an abundance of chromium available at the surface of the fine-grain alloy, chromia formed in the microcracks within the silica layer. As a result, the silica-coated, fine-grain alloy demonstrated superior oxidation resistance and excellent adhesion of the coating.

  2. 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.

  3. Moderate hypoxia followed by reoxygenation results in blood-brain barrier breakdown via oxidative stress-dependent tight-junction protein disruption.

    PubMed

    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 this

  4. 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

  5. Oxidative methane conversion in dielectric barrier discharge

    NASA Astrophysics Data System (ADS)

    Krawczyk, Krzysztof; Młotek, Michał; Ulejczyk, Bogdan; Pryciak, Krzysztof; Schmidt-Szałowski, Krzysztof

    2013-02-01

    A dielectric barrier discharge was used for the oxidative coupling of methane (OCM) with oxygen at the pressure of 1.2 bar. A dielectric barrier discharge (DBD) reactor was powered at the frequency of about 6 kHz. Molar ratio CH4/O2 in the inlet gas containing 50% or 25% of argon was 3, 6 and 12. The effects of temperature (110, 150 and 340 ◦C), gas flow rate, molar ratio of methane to oxygen on the overall methane and oxygen conversion and methane conversion to methanol, ethanol, hydrocarbons, carbon oxides and water were studied. In the studied system the increase of the temperature decreases the conversion of methane to methanol. The increase of the molar ratio of methane to oxygen increased the methane conversion to hydrocarbons and strongly decreased the methane conversion to alcohols. The conversion of methane to hydrocarbons increased and the conversion of methane to methanol decreased with the decrease of the gas flow rate from 2 to 1 NL/h. Contribution to the Topical Issue "13th International Symposium on High Pressure Low Temperature Plasma Chemistry (Hakone XIII)", Edited by Nicolas Gherardi, Henryca Danuta Stryczewska and Yvan Ségui.

  6. Polyelectrolyte/Graphene Oxide Barrier Film for Flexible OLED.

    PubMed

    Yang, Seung-Yeol; Park, Jongwhan; Kim, Yong-Seog

    2015-10-01

    Ultra-thin flexible nano-composite barrier layer consists of graphene oxide and polyelectrolyte was prepared using the layer-by-layer processing method. Microstructures of the barrier layer was optimized via modifying coating conditions and inducing chemical reactions. Although the barrier layer consists of hydrophilic polyelectrolyte was not effective in blocking the water vapor permeation, the chemical reduction of graphene oxide as well as conversion of polyelectrolyte to hydrophobic nature were very effective in reducing the permeation. PMID:26726415

  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. Oxidation behavior of a thermal barrier coating

    NASA Technical Reports Server (NTRS)

    Miller, R. A.

    1984-01-01

    Thermal barrier coatings, consisting of a plasma sprayed calcium silicate ceramic layer and a CoCrAlY or NiCrAlY bond coat, were applied on B-1900 coupons and cycled hourly in air in a rapid-response furnace to maximum temperatures of 1030, 1100, or 1160 C. Eight specimens were tested for each of the six conditions of bond-coat composition and temperature. Specimens were removed from test at the onset of failure, which was taken to be the formation of a fine surface crack visible at 10X magnification. Specimens were weighed periodically, and plots of weight gain vs time indicate that weight is gained at a parabolic rate after an initial period where weight was gained at a much greater rate. The high initial oxidation rate is thought to arise from the initially high surface area in the porous bond coat. Specimen life (time to first crack) was found to be a strong function of temperature. However, while test lives varied greatly with time, the weight gain at the time of specimen failure was quite insensitive to temperature. This indicates that there is a critical weight gain at which the coating fails when subjected to this test.

  9. Temperature dependent resistance of magnetic tunnel junctions as a quality proof of the barrier

    SciTech Connect

    Rudiger, U.; Calarco, R.; May, U.; Samm, K.; Hauch, J.; Kittur, H.; Sperlich, M.; Guntherodt, G.

    2001-06-01

    Tunnel junctions of Co(10 nm)/AlO{sub x} (nominally 2 nm)/Co(20 nm) have been prepared by molecular beam epitaxy applying a shadow mask technique in conjunction with an UV light-assisted oxidation process of the AlO{sub x} barrier. The quality of the AlO{sub x} barrier has been proven by x-ray photoelectron spectroscopy and temperature dependent tunneling magnetoresistance (TMR) measurements. Optimum-oxidized tunnel junctions show a TMR of 20% at 285 K and up to 36% at 100 K. At 285 K the TMR values as a function of oxidation time are not symmetric about the optimum time. For underoxidized junctions the TMR is reduced more strongly than for overoxidized junctions. The temperature dependence of the junction{close_quote}s resistance is a clear and reliable indicator whether pinholes (or imperfections) contribute to the conduction across the barrier. {copyright} 2001 American Institute of Physics.

  10. 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.

  11. Mechanisms of lung endothelial barrier disruption induced by cigarette smoke: role of oxidative stress and ceramides.

    PubMed

    Schweitzer, Kelly S; Hatoum, Hadi; Brown, Mary Beth; Gupta, Mehak; Justice, Matthew J; Beteck, Besem; Van Demark, Mary; Gu, Yuan; Presson, Robert G; Hubbard, Walter C; Petrache, Irina

    2011-12-01

    The epithelial and endothelial cells lining the alveolus form a barrier essential for the preservation of the lung respiratory function, which is, however, vulnerable to excessive oxidative, inflammatory, and apoptotic insults. Whereas profound breaches in this barrier function cause pulmonary edema, more subtle changes may contribute to inflammation. The mechanisms by which cigarette smoke (CS) exposure induce lung inflammation are not fully understood, but an early alteration in the epithelial barrier function has been documented. We sought to investigate the occurrence and mechanisms by which soluble components of mainstream CS disrupt the lung endothelial cell barrier function. Using cultured primary rat microvascular cell monolayers, we report that CS induces endothelial cell barrier disruption in a dose- and time-dependent manner of similar magnitude to that of the epithelial cell barrier. CS exposure triggered a mechanism of neutral sphingomyelinase-mediated ceramide upregulation and p38 MAPK and JNK activation that were oxidative stress dependent and that, along with Rho kinase activation, mediated the endothelial barrier dysfunction. The morphological changes in endothelial cell monolayers induced by CS included actin cytoskeletal rearrangement, junctional protein zonula occludens-1 loss, and intercellular gap formation, which were abolished by the glutathione modulator N-acetylcysteine and ameliorated by neutral sphingomyelinase inhibition. The direct application of ceramide recapitulated the effects of CS, by disrupting both endothelial and epithelial cells barrier, by a mechanism that was redox and apoptosis independent and required Rho kinase activation. Furthermore, ceramide induced dose-dependent alterations of alveolar microcirculatory barrier in vivo, measured by two-photon excitation microscopy in the intact rat. In conclusion, soluble components of CS have direct endothelial barrier-disruptive effects that could be ameliorated by glutathione

  12. Oxidation and degradation of thermal barrier coating systems

    NASA Astrophysics Data System (ADS)

    Haynes, James Allen

    Thermal barrier coatings (TBCs), which consist of an oxidation-resistant metallic bond coating overlaid with a thermally-insulating Ysb2Osb3-stabilized ZrOsb2 (YSZ) top coating, are used to protect superalloy hardware in gas turbine engines. Spallation of the YSZ is accelerated by growth of an interfacial Alsb2Osb3 scale at high temperatures. The mechanisms of oxidation-related degradation are not well understood for air plasma-sprayed (APS) TBCs, whereas Alsb2Osb3 thermomechanical failure is the dominant degradation mode in electron beam-physical vapor deposition (EB-PVD) TBCs. This work investigated the isothermal oxidation and thermocyclic degradation of various TBC systems; with particular emphasis on the growth kinetics, microstructures, flaw content, fracture behavior and micro-mechanical properties of the Alsb2Osb3 interfacial scales. The isothermal oxidation kinetics of plasma-sprayed NiCrAlY were not influenced by the presence of an APS YSZ top coating (at 1150sp°C). However, the isothermal oxidation rate constants of NiCoCrAlY bond coatings were accelerated by a factor of 2 (at 950, 1050 and 1150sp°C) when overlaid with a commercial EB-PVD TBC. Thermocyclic failure of APS TBCs occurred by progressive YSZ fracture and crack link-up. Severe fracture and buckling of the interfacial Alsb2Osb3 during thermal cycling did not induce rapid failure of APS TBCs. Evaluation of the interfacial Alsb2Osb3 scale microstructures (on APS TBCs) after thermal cycling revealed the following: thermocyclic damage occurred by both oxide-metal delamination and by internal fracture; Alsb2Osb3 scale crack healing by sintering occurred at 1150sp°C; surfaces with a sharp radius of curvature induced less Alsb2Osb3 damage than gradually convex surfaces; scale grain boundary void growth was accelerated by thermal cycling; and higher void contents were observed in scales which formed on convex surfaces. There were no significant changes in the hardness or Young's modulus of the Alsb2

  13. GUCY2C opposes systemic genotoxic tumorigenesis by regulating AKT-dependent intestinal barrier integrity.

    PubMed

    Lin, Jieru Egeria; Snook, Adam Eugene; Li, Peng; Stoecker, Brian Arthur; Kim, Gilbert Won; Magee, Michael Sullivan; Garcia, Alex Vladimir Mejia; Valentino, Michael Anthony; Hyslop, Terry; Schulz, Stephanie; Waldman, Scott Arthur

    2012-01-01

    The barrier separating mucosal and systemic compartments comprises epithelial cells, annealed by tight junctions, limiting permeability. GUCY2C recently emerged as an intestinal tumor suppressor coordinating AKT1-dependent crypt-villus homeostasis. Here, the contribution of GUCY2C to barrier integrity opposing colitis and systemic tumorigenesis is defined. Mice deficient in GUCY2C (Gucy2c(-/-)) exhibited barrier hyperpermeability associated with reduced junctional proteins. Conversely, activation of GUCY2C in mice reduced barrier permeability associated with increased junctional proteins. Further, silencing GUCY2C exacerbated, while activation reduced, chemical barrier disruption and colitis. Moreover, eliminating GUCY2C amplified, while activation reduced, systemic oxidative DNA damage. This genotoxicity was associated with increased spontaneous and carcinogen-induced systemic tumorigenesis in Gucy2c(-/-) mice. GUCY2C regulated barrier integrity by repressing AKT1, associated with increased junction proteins occludin and claudin 4 in mice and Caco2 cells in vitro. Thus, GUCY2C defends the intestinal barrier, opposing colitis and systemic genotoxicity and tumorigenesis. The therapeutic potential of this observation is underscored by the emerging clinical development of oral GUCY2C ligands, which can be used for chemoprophylaxis in inflammatory bowel disease and cancer. PMID:22384056

  14. Potential Dependence of Electrochemical Barriers from ab Initio Calculations.

    PubMed

    Chan, Karen; Nørskov, Jens K

    2016-05-01

    We present a simple and computationally efficient method to determine the potential dependence of the activation energies for proton-electron transfer from a single ab initio barrier calculation. We show that the potential dependence of the activation energy is given by the partial charge transferred at the transition state. The method is evaluated against the potential dependence determined explicitly through multiple calculations at varying potential. We show that the transfer coefficient is given by the charge transferred from the initial to transition state, which has significant implications for electrochemical kinetics. PMID:27088442

  15. Thermal expansion mismatch and oxidation in thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Chang, G. C.; Phucharoen, W.; Miller, R. A.

    1985-01-01

    Thermal barrier coatings (TBC) for advanced gas turbine blades have been under intensive development during the last several years. This investigation is intended to achieve a clearer understanding of the mechanical behavior of plasma sprayed zirconia-yttria TBCs, involving a nickle-chromium-aluminum bond coat. The near term objectives are to study the stress states in a relatively simple model TBC subjected to steady state thermal loading. The resulting thermal expansion mismatch and oxidation have been primary targets for the study. The finite element approach and the effects of thermal mismatch and oxidation are described. A proposed mechanism for oxidation induced coating failure is also presented.

  16. 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.

  17. Nitric Oxide Mediates Tightening of the Endothelial Barrier by Ascorbic Acid

    PubMed Central

    May, James M.; Qu, Zhi-chao

    2010-01-01

    Vitamin C, or ascorbic acid, decreases paracellular endothelial permeability in a process that requires rearrangement of the actin cytoskeleton. To define the proximal mechanism of this effect, we tested whether it might involve enhanced generation and/or sparing of nitric oxide (NO) by the vitamin. EA.hy926 endothelial cells cultured on semi-porous filter supports showed decreased endothelial barrier permeability to radiolabeled inulin in response to exogenous NO provided by the NO donor spermine NONOATE, as well as to activation of the downstream NO pathway by 8-bromo-cyclic GMP, a cell-penetrant cyclic GMP analog. Inhibition of endothelial nitric oxide synthase (eNOS) with Nω-nitro-L-arginine methyl ester increased endothelial permeability, indicating a role constitutive NO generation by eNOS in maintaining the permeability barrier. Inhibition of guanylate cyclase by 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one also increased endothelial permeability and blocked barrier tightening by spermine NONOATE. Loading cells with what are likely physiologic concentrations of ascorbate decreased endothelial permeability. This effect was blocked by inhibition of either eNOS or guanylate cyclase, suggesting that it involved generation of NO by eNOS and subsequent NO-dependent activation of guanylate cyclase. These results show that endothelial permeability barrier function depends on constitutive generation of NO and that ascorbate-dependent tightening of this barrier involves maintaining NO through the eNOS/guanylate cyclase pathway. PMID:21156160

  18. 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.

  19. Scalability of Schottky barrier metal-oxide-semiconductor transistors

    NASA Astrophysics Data System (ADS)

    Jang, Moongyu

    2016-05-01

    In this paper, the general characteristics and the scalability of Schottky barrier metal-oxide-semiconductor field effect transistors (SB-MOSFETs) are introduced and reviewed. The most important factors, i.e., interface-trap density, lifetime and Schottky barrier height of erbium-silicided Schottky diode are estimated using equivalent circuit method. The extracted interface trap density, lifetime and Schottky barrier height for hole are estimated as 1.5 × 1013 traps/cm2, 3.75 ms and 0.76 eV, respectively. The interface traps are efficiently cured by N2 annealing. Based on the diode characteristics, various sizes of erbium-silicided/platinum-silicided n/p-type SB-MOSFETs are manufactured and analyzed. The manufactured SB-MOSFETs show enhanced drain induced barrier lowering (DIBL) characteristics due to the existence of Schottky barrier between source and channel. DIBL and subthreshold swing characteristics are comparable with the ultimate scaling limit of double gate MOSFETs which shows the possible application of SB-MOSFETs in nanoscale regime.

  20. 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.

  1. 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.

  2. 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.

  3. Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Francillon, Wesley

    This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is

  4. Temperature-Dependent Photoluminescence of Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Jadhav, S. T.; Rajoba, S. J.; Patil, S. A.; Han, S. H.; Jadhav, L. D.

    2016-01-01

    Graphene oxide thin films have been deposited by spray pyrolysis using graphene oxide powder prepared by modified Hummers method. These thin films were characterized by different physico-chemical techniques. The x-ray diffraction studies revealed the structural properties of GO (graphene oxide) while the Raman spectrum showed the presence of D and G and two-dimensional bands. The D/G intensity ratio for spray-deposited GO film is 1.10. The x-ray photoelectron spectroscopy showed 67% and 33% atomic percentages of carbon and oxygen, respectively. The ratio of O1s/C1s was found to be 0.49. The temperature-dependent photoluminescence of GO thin film and GO solution showed a blue emission.

  5. 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.

  6. Role of atomic layer deposited aluminum oxide as oxidation barrier for silicon based materials

    SciTech Connect

    Fiorentino, Giuseppe Morana, Bruno; Forte, Salvatore; Sarro, Pasqualina Maria

    2015-01-15

    In this paper, the authors study the protective effect against oxidation of a thin layer of atomic layer deposited (ALD) aluminum oxide (Al{sub 2}O{sub 3}). Nitrogen doped silicon carbide (poly-SiC:N) based microheaters coated with ALD Al{sub 2}O{sub 3} are used as test structure to investigate the barrier effect of the alumina layers to oxygen and water vapor at very high temperature (up to 1000 °C). Different device sets have been fabricated changing the doping levels, to evaluate possible interaction between the dopants and the alumina layer. The as-deposited alumina layer morphology has been evaluated by means of AFM analysis and compared to an annealed sample (8 h at 1000 °C) to estimate the change in the grain structure and the film density. The coated microheaters are subjected to very long oxidation time in dry and wet environment (up to 8 h at 900 and 1000 °C). By evaluating the electrical resistance variation between uncoated reference devices and the ALD coated devices, the oxide growth on the SiC is estimated. The results show that the ALD alumina coating completely prevents the oxidation of the SiC up to 900 °C in wet environment, while an oxide thickness reduction of 50% is observed at 1000 °C compared to uncoated devices.

  7. Intracellular mediators of JAM-A–dependent epithelial barrier function

    PubMed Central

    Monteiro, Ana C.; Parkos, Charles A.

    2012-01-01

    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. PMID:22671597

  8. 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.

  9. Variable products in dielectric-barrier discharge assisted benzene oxidation.

    PubMed

    Dey, G R; Sharma, Asmita; Pushpa, K K; Das, Tomi Nath

    2010-06-15

    Atmospheric-pressure dielectric-barrier discharge (DBD) assisted control of benzene((g)) oxidation into different classes of products is presented in this study. The gas-phase products were directly analyzed online by GC-FID and GC-MS. In addition, a solid yellowish surface deposit also formed, which was dissolved in 10 mL ethanol after each 10 min DBD cycle for GC analyses. One of the gas-phase products, phenol was also separately collected and estimated by Folin-Ciocalteu's wet-colorimetric method. In the gas phase only phenol and biphenyl were detected at maximum total conversion of approximately 3%, while in the ethanolic solution furthermore 1,2- and 1,4-dihydroxybenzene, 2,2'-biphenol, 2- and 4-phenylphenol and 4-phenoxyphenol were estimated at microM to mM level, and reveal approximately 30% total conversion. Products' types hint at the phenyl radical as the primary precursor. However, with the use of mesoporous molecular sieve 10X packing in unison with DBD, while the concentrations of such phenolic products decreased drastically, a number of open chain and non-aromatic ethers, aldehydes and esters, and also naphthalene and biphenylene were formed. In addition to high DBD process efficiency, the latter results suggest modification of discharge characteristics, and also strong physicochemical effects of cavity size and surface property on the intermediate reactions therein. Thus, use of such packing highlights a novel and practical methodology for control of chemical reactions towards useful product types, vis-à-vis pollutant mitigation. PMID:20188466

  10. 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

  11. 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. PMID:26573561

  12. Angular confinement and direction-dependent transmission in graphene nanostructures with magnetic barriers

    NASA Astrophysics Data System (ADS)

    Masir, M. Ramezani; Vasilopoulos, P.; Matulis, A.; Peeters, F. M.

    2010-01-01

    We evaluate the transmission through magnetic barriers in graphene-based nanostructures. Several particular cases are considered: a magnetic step, single and double barriers, δ -function barriers as well as barrier structures with inhomogeneous magnetic field profiles but with average magnetic field equal to zero. The transmission exhibits a strong dependence on the direction of the incident wave vector. In general the resonant structure of the transmission is significantly more pronounced for (Dirac) electrons with linear spectrum compared to that for electrons with a parabolic one.

  13. 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.

  14. 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.

  15. In situ lifetimes and kinetics of a reductive whey barrier and an oxidative ORC barrier in the subsurface.

    PubMed

    Barcelona, M J; Xie, G

    2001-08-15

    Permeable reactive barriers (PRB) are being used to engineer favorable field conditions for in-situ remediation efforts. Two redox adjustment barriers were installed to facilitate a 10-month research effort on the fate and transport of MTBE (methyl tert-butyl ether) at a site called the Michigan Integrated Remediation Technology Laboratory (MIRTL). Thirty kilograms of whey were injected as a slurry into an unconfined aquifer to establish an upgradient reductive zone to reduce O2 concentration in the vicinity of a contaminant injection source. To minimize the impact of contaminant release, 363 kg of oxygen release compound (ORC) were placed in the aquifer as a downgradient oxidative barrier. Dissolved oxygen and other chemical species were monitored in the field to evaluate the effectiveness of this technology. A transient one-dimensional advective-dispersive-reaction (ADR) model was proposed to simulate the dissolved oxygen transport. The equations were solved with commonly encountered PRB initial and constant/variable boundary conditions. No similar previous solution was found in the literature. The in-situ lifetimes, based on variable source loading, were estimated to be 1,661 and 514 days for the whey barrier and ORC barrier, respectively. Estimates based on either maximum O2 consumption/production or measured O2 curves were found to under- or overestimate the lifetime of the barriers. The pseudo-first-order rate constant of whey depletion was estimated to be 0.303/d with a dissolution rate of 0.04/d. The oxygen release rate constant in the ORC barrier was estimated to be 0.03/d. This paper provides a means to design and predict the performance of reactive redox barriers, especially when only limited field data are available. PMID:11529581

  16. Nitric oxide synthase stimulates prostaglandin synthesis and barrier function in C. parvum-infected porcine ileum.

    PubMed

    Gookin, Jody L; Duckett, Laurel L; Armstrong, Martha U; Stauffer, Stephen H; Finnegan, Colleen P; Murtaugh, Michael P; Argenzio, Robert A

    2004-09-01

    Cell culture models implicate increased nitric oxide (NO) synthesis as a cause of mucosal hyperpermeability in intestinal epithelial infection. NO may also mediate a multitude of subepithelial events, including activation of cyclooxygenases. We examined whether NO promotes barrier function via prostaglandin synthesis using Cryptosporidium parvum-infected ileal epithelium in residence with an intact submucosa. Expression of NO synthase (NOS) isoforms was examined by real-time RT-PCR of ileal mucosa from control and C. parvum-infected piglets. The isoforms mediating and mechanism of NO action on barrier function were assessed by measuring transepithelial resistance (TER) and eicosanoid synthesis by ileal mucosa mounted in Ussing chambers in the presence of selective and nonselective NOS inhibitors and after rescue with exogenous prostaglandins. C. parvum infection results in induction of mucosal inducible NOS (iNOS), increased synthesis of NO and PGE2, and increased mucosal permeability. Nonselective inhibition of NOS (NG-nitro-L-arginine methyl ester) inhibited prostaglandin synthesis, resulting in further increases in paracellular permeability. Baseline permeability was restored in the absence of NO by exogenous PGE2. Selective inhibition of iNOS [L-N6-(1-iminoethyl)-L-lysine] accounted for approximately 50% of NOS-dependent PGE2 synthesis and TER. Using an entire intestinal mucosa, we have demonstrated for the first time that NO serves as a proximal mediator of PGE2 synthesis and barrier function in C. parvum infection. Expression of iNOS by infected mucosa was without detriment to overall barrier function and may serve to promote clearance of infected enterocytes. PMID:15155179

  17. A Septin-Dependent Diffusion Barrier at Dendritic Spine Necks

    PubMed Central

    Petersen, Jennifer D.; Racz, Bence; Sheng, Morgan; Choquet, Daniel

    2014-01-01

    Excitatory glutamatergic synapses at dendritic spines exchange and modulate their receptor content via lateral membrane diffusion. Several studies have shown that the thin spine neck impedes the access of membrane and solute molecules to the spine head. However, it is unclear whether the spine neck geometry alone restricts access to dendritic spines or if a physical barrier to the diffusion of molecules exists. Here, we investigated whether a complex of septin cytoskeletal GTPases localized at the base of the spine neck regulates diffusion across the spine neck. We found that, during development, a marker of the septin complex, Septin7 (Sept7), becomes localized to the spine neck where it forms a stable structure underneath the plasma membrane. We show that diffusion of receptors and bulk membrane, but not cytoplasmic proteins, is slower in spines bearing Sept7 at their neck. Finally, when Sept7 expression was suppressed by RNA interference, membrane molecules explored larger membrane areas. Our findings indicate that Sept7 regulates membrane protein access to spines. PMID:25494357

  18. COMPARISON OF OXYGEN TRANSFER TEST METHODS IN A TOTAL BARRIER OXIDATION DITCH CONFIGURATION

    EPA Science Inventory

    The Total Barrier Oxidation Ditch (TBOD), a recent development in oxidation ditch technology is described. The study was carried out in 1986 and 1987 for the purposes of: (1) evaluating the applicability of selected test procedures developed by the American Society of Civil Engin...

  19. Lie-algebraic approach for pricing moving barrier options with time-dependent parameters

    NASA Astrophysics Data System (ADS)

    Lo, C. F.; Hui, C. H.

    2006-11-01

    In this paper we apply the Lie-algebraic technique for the valuation of moving barrier options with time-dependent parameters. The value of the underlying asset is assumed to follow the constant elasticity of variance (CEV) process. By exploiting the dynamical symmetry of the pricing partial differential equations, the new approach enables us to derive the analytical kernels of the pricing formulae straightforwardly, and thus provides an efficient way for computing the prices of the moving barrier options. The method is also able to provide tight upper and lower bounds for the exact prices of CEV barrier options with fixed barriers. In view of the CEV model being empirically considered to be a better candidate in equity option pricing than the traditional Black-Scholes model, our new approach could facilitate more efficient comparative pricing and precise risk management in equity derivatives with barriers by incorporating term-structures of interest rates, volatility and dividend into the CEV option valuation model.

  20. 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. PMID:26979552

  1. Temperature-dependent characteristics of 4H—SiC junction barrier Schottky diodes

    NASA Astrophysics Data System (ADS)

    Chen, Feng-Ping; Zhang, Yu-Ming; Zhang, Yi-Men; Tang, Xiao-Yan; Wang, Yue-Hu; Chen, Wen-Hao

    2012-03-01

    The current—voltage characteristics of 4H—SiC junction barrier Schottky (JBS) diodes terminated by an offset field plate have been measured in the temperature range of 25-300 °C. An experimental barrier height value of about 0.5 eV is obtained for the Ti/4H—SiC JBS diodes at room temperature. A decrease in the experimental barrier height and an increase in the ideality factor with decreasing temperature are shown. Reverse recovery testing also shows the temperature dependence of the peak recovery current density and the reverse recovery time. Finally, a discussion of reducing the reverse recovery time is presented.

  2. 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.

  3. 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.

  4. 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

  5. Strain-dependent disruption of blood-cerebrospinal fluid barrier by Streptoccocus suis in vitro.

    PubMed

    Tenenbaum, Tobias; Adam, Rüdiger; Eggelnpöhler, Ingo; Matalon, David; Seibt, Annette; K Novotny, Gerd E; Galla, Hans-Joachim; Schroten, Horst

    2005-04-01

    Streptococcus suis capsular type 2 is an important agent of diseases including meningitis among pigs worldwide, and is also a zoonotic agent. The barrier function of the choroid plexus epithelium that constitutes the structural basis for the blood-cerebrospinal fluid (CSF) barrier has not been elucidated yet in bacterial meningitis. We investigated the influence of various S. suis isolates on the barrier function of cultured porcine choroid plexus epithelial cells with respect to the transepithelial resistance and paracellular [(3)H]-mannitol flux. Preferentially apical application of S. suis isolates significantly decreased transepithelial resistance and significantly increased paracellular [(3)H]-mannitol flux in a time-, dose- and strain-dependent manner. Viable S. suis isolates caused cytotoxicity determined by lactate dehydrogenase assay and electron microscopy, whereas S. suis sonicates and UV-inactivated S. suis did not cause cytotoxicity. The observed effects on porcine choroid plexus epithelial cells barrier function could not exclusively be ascribed to known virulence factors of S. suis such as suilysin. In conclusion, S. suis isolates induce loss of blood-cerebrospinal fluid barrier function in an in vitro model. Thus, S. suis may facilitate trafficking of bacteria and leucocytes across the blood-cerebrospinal fluid barrier. The underlying mechanisms for the barrier breakdown have yet to be determined. PMID:15780575

  6. Human skin penetration and local effects of topical nano zinc oxide after occlusion and barrier impairment.

    PubMed

    Leite-Silva, V R; Sanchez, W Y; Studier, H; Liu, D C; Mohammed, Y H; Holmes, A M; Ryan, E M; Haridass, I N; Chandrasekaran, N C; Becker, W; Grice, J E; Benson, H A E; Roberts, M S

    2016-07-01

    Public health concerns continue to exist over the safety of zinc oxide nanoparticles that are commonly used in sunscreen formulations. In this work, we assessed the effects of two conditions which may be encountered in everyday sunscreen use, occlusion and a compromised skin barrier, on the penetration and local toxicity of two topically applied zinc oxide nanoparticle products. Caprylic/capric triglyceride (CCT) suspensions of commercially used zinc oxide nanoparticles, either uncoated or with a silane coating, were applied to intact and barrier impaired skin of volunteers, without and with occlusion for a period of six hours. The exposure time was chosen to simulate normal in-use conditions. Multiphoton tomography with fluorescence lifetime imaging was used to noninvasively assess zinc oxide penetration and cellular metabolic changes that could be indicative of toxicity. We found that zinc oxide nanoparticles did not penetrate into the viable epidermis of intact or barrier impaired skin of volunteers, without or with occlusion. We also observed no apparent toxicity in the viable epidermis below the application sites. These findings were validated by ex vivo human skin studies in which zinc penetration was assessed by multiphoton tomography with fluorescence lifetime imaging as well as Zinpyr-1 staining and toxicity was assessed by MTS assays in zinc oxide treated skin cryosections. In conclusion, applications of zinc oxide nanoparticles under occlusive in-use conditions to volunteers are not associated with any measurable zinc oxide penetration into, or local toxicity in the viable epidermis below the application site. PMID:27131753

  7. 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.

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

    DOE PAGESBeta

    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 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

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

    PubMed Central

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

    2014-01-01

    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. PMID:25326583

  10. 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.

  11. 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.

  12. 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.

  13. Effects of angular dependence of surface diffuseness in deformed nuclei on Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Adamian, G. G.; Antonenko, N. V.; Malov, L. A.; Scamps, G.; Lacroix, D.

    2014-09-01

    The angular dependence of surface diffuseness is further discussed. The results of self-consistent calculations are compared with those obtained with the phenomenological mean-field potential. The rather simple parametrizations are suggested. The effects of surface polarization and hexadecapole deformation on the height of the Coulomb barrier are revealed.

  14. Tissue inhibitor of metalloproteinases 3-dependent microvascular endothelial cell barrier function is disrupted under septic conditions.

    PubMed

    Arpino, Valerie; Mehta, Sanjay; Wang, Lefeng; Bird, Ryan; Rohan, Marta; Pape, Cynthia; Gill, Sean E

    2016-06-01

    Sepsis is associated with dysfunction of microvascular endothelial cells (MVEC) leading to tissue edema and multiple organ dysfunction. Metalloproteinases can regulate MVEC function through processing of cell surface proteins, and tissue inhibitor of metalloproteinases 3 (TIMP3) regulates metalloproteinase activity in the lung following injury. We hypothesize that TIMP3 promotes normal pulmonary MVEC barrier function through inhibition of metalloproteinase activity. Naive Timp3(-/-) mice had significantly higher basal pulmonary microvascular Evans blue (EB) dye-labeled albumin leak vs. wild-type (WT) mice. Additionally, cecal-ligation/perforation (CLP)-induced sepsis significantly increased pulmonary microvascular EB-labeled albumin leak in WT but not Timp3(-/-) mice. Similarly, PBS-treated isolated MVEC monolayers from Timp3(-/-) mice displayed permeability barrier dysfunction vs. WT MVEC, evidenced by lower transendothelial electrical resistance and greater trans-MVEC flux of fluorescein-dextran and EB-albumin. Cytomix (equimolar interferon γ, tumor necrosis factor α, and interleukin 1β) treatment of WT MVEC induced significant barrier dysfunction (by all three methods), and was associated with a time-dependent decrease in TIMP3 mRNA and protein levels. Additionally, basal Timp3(-/-) MVEC barrier dysfunction was associated with disrupted MVEC surface VE-cadherin localization, and both barrier dysfunction and VE-cadherin localization were rescued by treatment with GM6001, a synthetic metalloproteinase inhibitor. TIMP3 promotes normal MVEC barrier function, at least partially, through inhibition of metalloproteinase-dependent disruption of adherens junctions, and septic downregulation of TIMP3 may contribute to septic MVEC barrier dysfunction. PMID:26993226

  15. 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. PMID:23426527

  16. 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.

  17. Strong, self-standing oxygen barrier films from nanocelluloses modified with regioselective oxidative treatments.

    PubMed

    Sirviö, Juho Antti; Kolehmainen, Aleksi; Visanko, Miikka; Liimatainen, Henrikki; Niinimäki, Jouko; Hormi, Osmo E O

    2014-08-27

    In this work, three self-standing nanocellulose films were produced from birch pulp using regioselective oxidation and further derivatization treatments. The modified celluloses were synthesized using periodate oxidation, followed by chlorite oxidation, bisulfite addition, or reductive amination with amino acid taurine, which resulted in dicarboxylic acid cellulose (DCC), α-hydroxy sulfonic acid cellulose (HSAC), and taurine-modified cellulose (TC), respectively. The nanocelluloses were fabricated by mechanical disintegration using high-pressure homogenization. Mechanical and barrier properties of the nanocellulose films were characterized. Two (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) oxidation-based nanocellulose films were also produced, and their properties were compared to the periodate-based nanocellulose films. All of the periodate-based nanocellulose films showed high tensile strength (130-163 MPa) and modulus (19-22 GPa). Oxygen barrier properties of the films were superior to many synthetic and composite materials; in particular, the nanofibrillated DCC films had oxygen permeability as low as 0.12 cm(3) μm/(m(2) d kPa) at 50% relative humidity. Compared to films of TEMPO-oxidized nanocelluloses, all of the periodate-based nanocellulose films had similar or even better mechanical and barrier properties, demonstrating versatility of periodate oxidation to obtain nanocellulose films with adjustable properties. Also, for the first time, amino-acid-based cellulose modification was used in the production of nanocellulose. PMID:25089516

  18. 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.

  19. Impermeable barrier films and protective coatings based on reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Su, Y.; Kravets, V. G.; Wong, S. L.; Waters, J.; Geim, A. K.; Nair, R. R.

    2014-09-01

    Flexible barrier films preventing permeation of gases and moistures are important for many industries ranging from food to medical and from chemical to electronic. From this perspective, graphene has recently attracted particular interest because its defect-free monolayers are impermeable to all atoms and molecules. However, it has been proved to be challenging to develop large-area defectless graphene films suitable for industrial use. Here we report barrier properties of multilayer graphitic films made by gentle chemical reduction of graphene oxide laminates with hydroiodic and ascorbic acids. They are found to be highly impermeable to all gases, liquids and aggressive chemicals including, for example, hydrofluoric acid. The exceptional barrier properties are attributed to a high degree of graphitization of the laminates and little structural damage during reduction. This work indicates a close prospect of graphene-based flexible and inert barriers and protective coatings, which can be of interest for numerous applications.

  20. 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

  1. 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.

  2. Polymer-Derived Ceramics as Innovative Oxidation Barrier Coatings for Mo-Si-B Alloys

    NASA Astrophysics Data System (ADS)

    Hasemann, Georg; Baumann, Torben; Dieck, Sebastian; Rannabauer, Stefan; Krüger, Manja

    2015-04-01

    A preceramic polymer precursor, perhydropolysilazane, is used to investigate its function as a new type of oxidation barrier coating on Mo-Si-B alloys. After dip-coating and pyrolysis at 1073 K (800 °C), dense and well-adhering SiON ceramic coatings could be achieved, which were investigated by SEM and cyclic oxidation tests at 1073 K and 1373 K (800 °C and 1100 °C). The coating is promising in reducing the mass loss during the initial stage of oxidation exposure at 1373 K (1100 °C) significantly.

  3. 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.

  4. Investigation of humidity-dependent size control of local anodic oxidation on graphene by using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Ko, Seoknam; Lee, Seong jun; Son, Maengho; Ahn, Doyeol; Lee, Seung-Woong

    2015-02-01

    We demonstrate nanoscale local anodic oxidation (LAO) patterning on few-layer graphene by using an atomic force microscope (AFM) at room temperature under a normal atmosphere. We focus on the humidity dependency of nanoscale oxidation of graphene. The relations between the oxidation size and the setting values of the AFM, such as the set point, tip speed, and the humidity, are observed. By changing these values, proper parameters were found to produce features with on-demand size. This technique provides an easy way for graphene oxide lithography without any chemical resists. We obtained oxidation sizes down to 50 nm with a 6-nm-high oxide barrier line by using a 0.1- μm/s tip scanning speed. We also obtained micrometer-sized symbols on a graphene flake. We attribute the bumps of oxidized graphene in the graphene layer to local anodic oxidation on graphenes surface and to an incorporation of oxygen ions into the graphene lattice.

  5. 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

  6. 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).

  7. 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.

  8. 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

  9. 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

    2016-01-01

    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

  10. [Inhalation of nitric oxide - dependence: case report

    PubMed

    Carvalho, W B; Matsumoto, T; Horita, S M; Almeida, N M; Martins, F R

    2000-01-01

    OBJECTIVE: Describe the hemodynamic response with rebound of pulmonary hypertension after withdrawal of inhaled nitric oxide (NO) in a pediatric patient with acute respiratory distress syndrome (ARDS). METHODS: Case report of a child with ARDS and pulmonary hypertension evaluated through ecocardiografic with dopller, receiving inhaled NO for a period of 21 days. RESULTS: There was a decrease of the pulmonary artery pressure (PAP) from 52 mmHg to 44 mmHg after the initial titulation of NO inhalation dose. After the withdrawal of inhaled NO an elevation of PAP was observed (55 mmHg). It was necessary to reinstall the inhaled NO to obtain a more appropriate value (34 mmHg). A new attempt of interruption of the inhaled NO after prolonged inhalation (20 days) resulted in a new clinic worsening and increase of PAP, with the indication to reinstall the inhaled NO. In the 24th day of permanence in the intensive care unit the patient died due to multiple organ dysfunction. CONCLUSIONS: The possibility of pulmonary hypertension rebound after withdrawal of inhaled NO is a complication that may have important clinical implications for patients who need a prolonged treatment with NO. This case report emphasizes these implications. PMID:14647690

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

    DOE PAGESBeta

    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

  12. RF-sputter-deposited magnesium oxide films as high-quality adjustable tunnel barriers

    SciTech Connect

    Villegier, J.C.; Radparvar, M.; Yu, L.S.; Faris, S.M.

    1989-03-01

    High quality RF-sputtered MgO films are used as tunnel barriers to fabricate small area, niobium nitride Josephson tunnel junctions. A magnesium oxide barrier deposited as a single layer, or as a multilayer film, results in devices with similar characteristics. Annealing trilayers at temperatures in excess of 250/sup 0/C for several hours decrease junction current density and improve device quality presumably by increasing barrier heights through reducing resonant tunneling states. A self-aligned process utilizing only two mask levels is used to produce junctions as small as 0.5 ..mu..m/sup 2/ with excellent critical current uniformity. These junctions exhibit energy gaps of 5.1 mV and low subgap currents at current densities in excess of 1000 A/cm/sup 2/ which make them suitable for a variety of applications such as SIS mixers and logic circuits.

  13. 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.

  14. Coefficient of thermal expansion dependent thermal stress analysis of thermal barrier coatings (TBCs) using finite element model

    NASA Astrophysics Data System (ADS)

    Coker, Omotola

    Thermal barrier coatings (TBCs) are highly sophisticated micro scale ceramic insulation applied on high temperature components such as gas turbine blades. TBCs create a large temperature drop between the gas turbine environment and the underlying metal blades. TBC lifetime is finite and influenced by several factors such as: Bond Coat (BC) oxidation, BC roughness, Coefficient of thermal expansion (CTE) mismatch between the layers, and creep properties of the TBC system. However, there is a lack of reliable methods of TBC life prediction which result in under utilization of these coatings. This research study focuses on modeling the steady state thermal stresses in TBC systems of various oxide thicknesses, and BC roughness, using Finite Element Analysis (FEA). The model factors into it the temperature dependent thermo mechanical properties of each layer, as well as the creep properties. The steady state model results show similar results to the existing transient models: an increase in tensile stresses as the oxide thickness increases, an increase in tensile stresses with BC roughness and stress relaxation in the ceramic BC interface due to creep. It also shows in each model, initially compressive stresses in the BC - Top Coat (TC) interface, and its evolution into higher tensile stresses which lead to crack formation and ultimately failure of the TBC by spallation.

  15. 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.

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

    DOE PAGESBeta

    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.; et al

    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

  17. 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

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

    PubMed Central

    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.

    2014-01-01

    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. PMID:24829380

  19. 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. PMID:24829380

  20. 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. PMID:24359869

  1. Modeling of Schottky Barrier Modulation due to Oxidation at Metallic Electrode and Semiconducting Carbon Nanotube Junction

    NASA Technical Reports Server (NTRS)

    Yamada, Toshishige; Biegel, Bryan (Technical Monitor)

    2003-01-01

    A model is proposed for the previously reported lower Schottky barrier for holes PHI (sub bH) in air than in vacuum at a metallic electrode - semiconducting carbon nanotube (CNT) junction. We assume that there is a transition region between the electrode and the CNT, and an appreciable potential can drop there. The role of the oxidation is to increase this potential drop with negatively charged oxygen molecules on the CNT, leading to lower PHI(sub Bh) after oxidation. The mechanism prevails in both p- and n-CNTs, and the model consistently explains the key experimental findings.

  2. 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.

  3. Chronic Kidney Disease Induced Intestinal Mucosal Barrier Damage Associated with Intestinal Oxidative Stress Injury

    PubMed Central

    Yu, Chao; Wang, Qiang; Zhou, Chunyu; Kang, Xin; Zhao, Shuang; Liu, Shuai; Fu, Huijun; Yu, Zhen; Peng, Ai

    2016-01-01

    Background. To investigate whether intestinal mucosal barrier was damaged or not in chronic kidney disease progression and the status of oxidative stress. Methods. Rats were randomized into two groups: a control group and a uremia group. The uremia rat model was induced by 5/6 kidney resection. In postoperative weeks (POW) 4, 6, 8, and 10, eight rats were randomly selected from each group to prepare samples for assessing systemic inflammation, intestinal mucosal barrier changes, and the status of intestinal oxidative stress. Results. The uremia group presented an increase trend over time in the serum tumor necrosis factor-alpha, interleukin-6 (IL-6) and IL-10, serum D-lactate and diamine oxidase, and intestinal permeability, and these biomarkers were significantly higher than those in control group in POW 8 and/or 10. Chiu's scores in uremia group were also increased over time, especially in POW 8 and 10. Furthermore, the intestinal malondialdehyde, superoxide dismutase, and glutathione peroxidase levels were significantly higher in uremia group when compared with those in control group in POW 8 and/or 10. Conclusions. The advanced chronic kidney disease could induce intestinal mucosal barrier damage and further lead to systemic inflammation. The underlying mechanism may be associated with the intestinal oxidative stress injury. PMID:27493661

  4. 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.

  5. 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

  6. Analytical energy-barrier-dependent Voc model for amorphous silicon solar cells

    NASA Astrophysics Data System (ADS)

    Castro-Carranza, A.; Nolasco, J. C.; Reininghaus, N.; Geißendörfer, S.; Vehse, M.; Parisi, J.; Gutowski, J.; Voss, T.

    2016-07-01

    We show that the open circuit voltage (Voc) in hydrogenated amorphous silicon (a-Si:H) solar cells can be described by an analytical energy-barrier-dependent equation, considering thermionic emission as the physical mechanism determining the recombination current. For this purpose, the current-voltage characteristics of two device structures, i.e., a-Si:H(n)/a-Si:H(i)/a-Si:H(p)/AZO p-i-n solar cells with different p-doping concentrations and a-Si:H(n)/a-Si:H(i)/AZO Schottky structures with different intrinsic layer thicknesses, were analyzed in dark and under illumination, respectively. The calculated barrier in the p-i-n devices is consistent with the difference between the work function of the p-layer and the conduction band edge of the i-layer at the interface in thermal equilibrium.

  7. Spin-dependent shot noise in diluted magnetic semiconductor/semiconductor heterostructures with a nonmagnetic barrier

    NASA Astrophysics Data System (ADS)

    Wu, Shuang; Guo, Yong

    2014-05-01

    We investigate quantum size effect on the spin-dependent shot noise in the diluted magnetic semiconductor (DMS)/semiconductor heterostructure with a nonmagnetic semiconductor (NMS) barrier in the presence of external magnetic and electric fields. The results demonstrate that the NMS barrier plays a quite different role from the DMS layer in the electron transport process. It is found that spin-down shot noise shows relatively regular oscillations as the width of DMS layer increases, while the spin-up shot noise deceases monotonically. However, as the width of NMS layer increases, the spin-down shot noise displays irregular oscillations at first and then decreases while the spin-up shot noise decreases at a quite different rate. The results indicate that the shot noise can be used as a sensitive probe in detecting material type and its size.

  8. Understanding the Barriers to Use of Free, Proactive Telephone Counseling for Tobacco Dependence

    PubMed Central

    Sheffer, Christine E.; Brackman, Sharon L.; Cottoms, Naomi; Olsen, Mary

    2012-01-01

    We sought to gain an empirical and practical understanding of the barriers experienced by Arkansas Mississippi Delta residents to using the free telephone counseling (quitline) for tobacco dependence. Barriers included lack of knowledge about the quitline, lack of trust in the providers, as well as multiple root causes to seeking and achieving abstinence from tobacco including issues related to the poor socio-economic context and concerns about negative health effects of quitting. A strong belief in the role of faith in the process of quitting was expressed. Participants suggested strategies for increasing knowledge and trust levels, but were not hopeful about addressing root causes. Given the considerable resources being allocated to quitlines and the burden of tobacco use and disease in lower socioeconomic and minority groups, understanding utilization of quitlines by these groups has implications for policy development, the promotion of quitlines, and the provision of alternate tobacco treatment services. PMID:21464470

  9. 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

  10. Size dependent reduction-oxidation-reduction behaviour of cobalt oxide nanocrystals.

    PubMed

    Sadasivan, Sajanikumari; Bellabarba, Ronan M; Tooze, Robert P

    2013-11-21

    Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal particles led to solid spheres, hollow spheres or core-shell structures depending on the size of the initial metal particle. Further re-reduction of the oxidized structures was also observed to be size dependent. The hollow oxide shells formed by the large particles (29 nm) fragmented into smaller particles on reduction, while the hollow shells of the medium sized particles (11 nm) did not re-disperse on further reduction. Similarly, no re-dispersion was observed in the case of the small particles (6 nm). This model study provides useful insights into the size dependent behavior of metal/metal oxide particles during oxidation/reduction. This has important implications in petrochemical industry where cobalt is used as a catalyst in the Fischer-Tropsch process. PMID:24065040

  11. Magnitude-dependent regulation of pulmonary endothelial cell barrier function by cyclic stretch.

    PubMed

    Birukov, Konstantin G; Jacobson, Jeffrey R; Flores, Alejandro A; Ye, Shui Q; Birukova, Anna A; Verin, Alexander D; Garcia, Joe G N

    2003-10-01

    Ventilator-induced lung injury syndromes are characterized by profound increases in vascular leakiness and activation of inflammatory processes. To explore whether excessive cyclic stretch (CS) directly causes vascular barrier disruption or enhances endothelial cell sensitivity to edemagenic agents, human pulmonary artery endothelial cells (HPAEC) were exposed to physiologically (5% elongation) or pathologically (18% elongation) relevant levels of strain. CS produced rapid (10 min) increases in myosin light chain (MLC) phosphorylation, activation of p38 and extracellular signal-related kinase 1/2 MAP kinases, and actomyosin remodeling. Acute (15 min) and chronic (48 h) CS markedly enhanced thrombin-induced MLC phosphorylation (2.1-fold and 3.2-fold for 15-min CS at 5 and 18% elongation and 2.1-fold and 3.1-fold for 48-h CS at 5 and 18% elongation, respectively). HPAEC preconditioned at 18% CS, but not at 5% CS, exhibited significantly enhanced thrombin-induced reduction in transendothelial electrical resistance but did not affect barrier protective effect of sphingosine-1-phosphate (0.5 microM). Finally, expression profiling analysis revealed a number of genes, including small GTPase rho, apoptosis mediator ZIP kinase, and proteinase activated receptor-2, to be regulated by CS in an amplitude-dependent manner. Thus our study demonstrates a critical role for the magnitude of CS in regulation of agonist-mediated pulmonary endothelial cell permeability and strongly suggests phenotypic regulation of HPAEC barrier properties by CS. PMID:12639843

  12. Graphene-graphene oxide-graphene hybrid nanopapers with superior mechanical, gas barrier and electrical properties

    NASA Astrophysics Data System (ADS)

    Ouyang, Xilian; Huang, Wenyi; Cabrera, Eusebio; Castro, Jose; Lee, L. James

    2015-01-01

    Hybrid nanopaper-like thin films with a graphene oxide (GO) layer sandwiched by two functionalized graphene (GP-SO3H) layers were successfully prepared from oxidized graphene and benzene sulfonic modified graphene. The hybrid graphene-graphene oxide-graphene (GP-GO-GP) nanopapers showed combination of high mechanic strength and good electrical conductivity, leading to desirable electromagnetic interference shielding performance, from the GP-SO3H layers, and superior gas diffusion barrier provided by the GO layer. These GP-GO-GP nanopapers can be readily coated onto plastic and composite substrates by thermal lamination and injection molding for various industrial applications such as fuel cell and natural gas containers.

  13. Oxidation resistance of tantalum-ruthenium dioxide diffusion barrier for memory capacitor bottom electrodes

    NASA Astrophysics Data System (ADS)

    Yoon, Dong-Soo; Baik, Hong Koo; Lee, Sung-Man; Park, Chang-Soo; Lee, Sang-In

    1998-07-01

    The effect of the RuO2 addition into a Ta film on the oxidation resistance of a diffusion barrier for the Ta+RuO2/Si system was investigated. The Ta+RuO2/Si system was sustained up to 800 °C without an increase in resistivity, while the Ta/Si structure completely degraded after annealing at 450 °C. The Ta+RuO2 diffusion barrier showed an amorphous microstructure for an as-deposited state and formed a conductive RuO2 phase after annealing. Ta was sufficiently bound to oxygen of RuO2 for an as-deposited state, but RuO2 was divided into Ru and Ru-O binding states. Ta-O bonds showed a little change compared to the as-deposited state with increasing annealing temperature, whereas Ru-O bonds significantly increased. Therefore, the Ta layer deposited by the RuO2 addition effectively prevented the indiffusion of oxygen up to 800 °C and its oxidation resistance was superior to those of polycrystalline nitride (TiN, TaN) and ternary amorphous (TaSiN) barriers reported by others.

  14. Voltage-controlled oxide barriers in organic/hybrid spin valves based on tunneling anisotropic magnetoresistance

    NASA Astrophysics Data System (ADS)

    Grünewald, M.; Homonnay, N.; Kleinlein, J.; Schmidt, G.

    2014-11-01

    Resistive switching, i.e., the remanent (reversible) change of a device's resistance, is a widely investigated phenomenon as it holds the prospect for realizing high density memory devices. Resistive switching has also been observed in organic semiconductors; however, a clear understanding of the underlying physics could not yet be obtained. Possible options are for example interface effects at the electrodes or the formation and destruction of filaments. Here we present resistive switching in an organic spin valve based on tunneling anisotropic magnetoresistance. Similar to experiments in conventional spin-valve devices with two ferromagnetic electrodes we observe a modulation of the magnetoresistance by the electrical switching. However, as the magnetoresistance effect's origin is unambiguously clear, which is not always the case for effects in conventional structures, it can be exploited to prove that a tunnel barrier exists at the interface between the ferromagnetic oxide electrode and the organic semiconductor. Furthermore our experiments reveal that this barrier is reversibly modified during the switching, which causes both the change in magnetoresistance and total device resistance. Quantitative analysis indicates that the barrier is situated in the oxide layer. A phenomenological model provides a full description of the microscopic processes involved in the resistive switching.

  15. 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.

  16. 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

  17. Adhesion Issues with Polymer/Oxide Barrier Coatings on Organic Displays

    SciTech Connect

    Matson, Dean W.; Martin, Peter M.; Graff, Gordon L.; Gross, Mark E.; Burrows, Paul E.; Bennett, Wendy D.; Hall, Michael G.; Mast, Eric S.; Bonham, Charles C.; Zumhoff, Mac R.; Rutherford, Nicole M.; Moro, Lorenza; Rosenblum, Martin; Praino, Robert F.; Visser, Robert J.

    2005-01-01

    Multilayer polymer/oxide coatings are being developed to protect sensitive organic display devices, such as OLEDs, from oxygen and water vapor permeation. The coatings have permeation levels ~ 10-6 g/m2/d for water vapor and ~10-6 cc/m2/d for oxygen, and are deposited by vacuum polymer technology. The coatings consist of either a base Al2O3 or acrylate polymer adhesion layer followed by alternating Al2O3/polymer layers. The polymer is used to decouple the 30 nm-thick Al2O3 barrier layers. Adhesion of the barrier coating to the substrate and display device is critical for the operating lifetime of the device. The substrate material could be any transparent flexible plastic. The coating technology can also be used to encapsulate organic-based electronic devices to protect them from atmospheric degradation. Plasma pretreatment is also needed for good adhesion to the substrate, but if it is too aggressive, it will damage the organic display device. We report on the effects of plasma treatment on the adhesion of barrier coatings to plastic substrates and the performance of OLED devices after plasma treatment and barrier coating deposition. We find that initial OLED performance is not significantly affected by the deposition process and plasma treatment, as demonstrated by luminosity and I-V curves.

  18. Fluence dependence of deuterium retention in oxidized SS-316

    NASA Astrophysics Data System (ADS)

    Oya, Yasuhisa; Suzuki, Sachiko; Matsuyama, Masao; Hayashi, Takumi; Yamanishi, Toshihiko; Asakura, Yamato; Okuno, Kenji

    2011-10-01

    The ion fluence dependence of deuterium retention in SS-316 during oxidation at a temperature of 673 K was studied to evaluate the dynamics of deuterium retention in the oxide layer of SS-316. The correlation between the chemical state of stainless steel and deuterium retention was evaluated using XPS and TDS. It was found that the major deuterium desorption temperatures were located at around 660 K and 935 K, which correspond to the desorption of deuterium trapped as hydroxide. The deuterium retention increased with increasing deuterium ion fluence, since the deuterium retention as hydroxide increased significantly. However, retention saturated at an ion fluence of ˜2.5 × 10 21 D + m -2. The XPS result showed that FeOOD was formed on the surface, although pure Fe also remained in the oxide layer. These facts indicate the nature of the oxide layer have a key role in deuterium trapping behavior.

  19. Ga0.5In0.5P Barrier Layer for Wet Oxidation of AlAs

    NASA Astrophysics Data System (ADS)

    Lee, Shih-Chang; Lee, Wei-I

    2000-05-01

    We study the stability of Ga0.5In0.5P and Al0.4Ga0.6As barrier layers for wet thermal oxidation of AlAs on GaAs. Samples with a Ga0.5In0.5P or Al0.4Ga0.6As barrier layer are oxidized in a water vapor environment under various oxidation conditions. The results of photoluminescence and secondary-ion mass spectrometry (SIMS) depth profile measurements indicate that the Ga0.5In0.5P barrier layer is more stable than the Al0.4Ga0.6As layer at higher oxidation temperatures and longer periods of oxidation time.

  20. 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.

  1. Oxidative stress and blood-brain barrier dysfunction under particular consideration of matrix metalloproteinases.

    PubMed

    Lehner, Christine; Gehwolf, Renate; Tempfer, Herbert; Krizbai, Istvan; Hennig, Bernhard; Bauer, Hans-Christian; Bauer, Hannelore

    2011-09-01

    A cell's "redox" (oxidation and reduction) state is determined by the sum of all redox processes yielding reactive oxygen species (ROS), reactive nitrogen species (RNS), and other reactive intermediates. Low amounts of ROS/RNS are generated by different mechanisms in every cell and are important regulatory mediators in many signaling processes (redox signaling). When the physiological balance between the generation and elimination of ROS/RNS is disrupted, oxidative/nitrosative stress with persistent oxidative damage of the organism occurs. Oxidative stress has been suggested to act as initiator and/or mediator of many human diseases. The cerebral vasculature is particularly susceptible to oxidative stress, which is critical since cerebral endothelial cells play a major role in the creation and maintenance of the blood-brain barrier (BBB). This article will only contain a focused introduction on the biochemical background of redox signaling, since this has been reported already in a series of excellent recent reviews. The goal of this work is to increase the understanding of basic mechanisms underlying ROS/RNS-induced BBB disruption, with a focus on the role of matrix metalloproteinases, which, after all, appear to be a key mediator in the initiation and progression of BBB damage elicited by oxidative stress. PMID:21294658

  2. 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. PMID:16148002

  3. Removal Of Nitric Oxide From Different Mixtures Of Gases Using Dielectric Barrier Discharge

    SciTech Connect

    Hashim, Siti Aiasah; San, Wong Chiow; Abas, Radzi

    2009-07-07

    Dielectric barrier discharge (DBD) is employed in this project as the processing medium to remove nitric oxide in gas stream. Gas stream containing different components was released continuously into a series of dielectric barrier discharge cells and the output gas was analyzed using a chemiluminescence's type NO analyzer. Almost complete removal (more than 99%) of NO was observed when the gas stream contained only NO and nitrogen. In the presence of SO{sub 2}, the removal rate was decreased to as low as 70%. Adding air into the stream gave a more erratic results. The removal rate was also affected by the number of DBD cell used and the flow rate of the input gas. However, In this paper, only results using 2 cells whilst varying the flow rate are presented.

  4. Size dependent reduction-oxidation-reduction behaviour of cobalt oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Sadasivan, Sajanikumari; Bellabarba, Ronan M.; Tooze, Robert P.

    2013-10-01

    Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal particles led to solid spheres, hollow spheres or core-shell structures depending on the size of the initial metal particle. Further re-reduction of the oxidized structures was also observed to be size dependent. The hollow oxide shells formed by the large particles (29 nm) fragmented into smaller particles on reduction, while the hollow shells of the medium sized particles (11 nm) did not re-disperse on further reduction. Similarly, no re-dispersion was observed in the case of the small particles (6 nm). This model study provides useful insights into the size dependent behavior of metal/metal oxide particles during oxidation/reduction. This has important implications in petrochemical industry where cobalt is used as a catalyst in the Fischer-Tropsch process.Morphologically similar cobalt oxide nanoparticles (Co3O4) of four different sizes (3 nm, 6 nm, 11 nm and 29 nm) with narrow size distribution were prepared by subtle variation of synthesis conditions. These nanoparticles were used as model materials to understand the structural and morphological changes that occur to cobalt oxide during sequential reduction, oxidation and further re-reduction process as a function of the initial size of cobalt oxide. On reduction, spherical cobalt nanoparticles were obtained independent of the original size of cobalt oxide. In contrast, subsequent oxidation of the metal

  5. 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.

  6. Myeloperoxidase-Derived Oxidants Induce Blood-Brain Barrier Dysfunction In Vitro and In Vivo

    PubMed Central

    Üllen, Andreas; Singewald, Evelin; Konya, Viktoria; Fauler, Günter; Reicher, Helga; Nusshold, Christoph; Hammer, Astrid; Kratky, Dagmar; Heinemann, Akos; Holzer, Peter; Malle, Ernst; Sattler, Wolfgang

    2013-01-01

    Peripheral leukocytes can exacerbate brain damage by release of cytotoxic mediators that disrupt blood-brain barrier (BBB) function. One of the oxidants released by activated leukocytes is hypochlorous acid (HOCl) formed via the myeloperoxidase (MPO)-H2O2-Cl− system. In the present study we examined the role of leukocyte activation, leukocyte-derived MPO and MPO-generated oxidants on BBB function in vitro and in vivo. In a mouse model of lipopolysaccharide (LPS)-induced systemic inflammation, neutrophils that had become adherent released MPO into the cerebrovasculature. In vivo, LPS-induced BBB dysfunction was significantly lower in MPO-deficient mice as compared to wild-type littermates. Both, fMLP-activated leukocytes and the MPO-H2O2-Cl− system inflicted barrier dysfunction of primary brain microvascular endothelial cells (BMVEC) that was partially rescued with the MPO inhibitor 4-aminobenzoic acid hydrazide. BMVEC treatment with the MPO-H2O2-Cl− system or activated neutrophils resulted in the formation of plasmalogen-derived chlorinated fatty aldehydes. 2-chlorohexadecanal (2-ClHDA) severely compromised BMVEC barrier function and induced morphological alterations in tight and adherens junctions. In situ perfusion of rat brain with 2-ClHDA increased BBB permeability in vivo. 2-ClHDA potently activated the MAPK cascade at physiological concentrations. An ERK1/2 and JNK antagonist (PD098059 and SP600125, respectively) protected against 2-ClHDA-induced barrier dysfunction in vitro. The current data provide evidence that interference with the MPO pathway could protect against BBB dysfunction under (neuro)inflammatory conditions. PMID:23691142

  7. 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

  8. 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.

  9. Drugs of abuse and blood-brain barrier endothelial dysfunction: A focus on the role of oxidative stress.

    PubMed

    Sajja, Ravi K; Rahman, Shafiqur; Cucullo, Luca

    2016-03-01

    Psychostimulants and nicotine are the most widely abused drugs with a detrimental impact on public health globally. While the long-term neurobehavioral deficits and synaptic perturbations are well documented with chronic use of methamphetamine, cocaine, and nicotine, emerging human and experimental studies also suggest an increasing incidence of neurovascular complications associated with drug abuse. Short- or long-term administration of psychostimulants or nicotine is known to disrupt blood-brain barrier (BBB) integrity/function, thus leading to an increased risk of brain edema and neuroinflammation. Various pathophysiological mechanisms have been proposed to underlie drug abuse-induced BBB dysfunction suggesting a central and unifying role for oxidative stress in BBB endothelium and perivascular cells. This review discusses drug-specific effects of methamphetamine, cocaine, and tobacco smoking on brain microvascular crisis and provides critical assessment of oxidative stress-dependent molecular pathways focal to the global compromise of BBB. Additionally, given the increased risk of human immunodeficiency virus (HIV) encephalitis in drug abusers, we have summarized the synergistic pathological impact of psychostimulants and HIV infection on BBB integrity with an emphasis on unifying role of endothelial oxidative stress. This mechanistic framework would guide further investigations on specific molecular pathways to accelerate therapeutic approaches for the prevention of neurovascular deficits by drugs of abuse. PMID:26661236

  10. 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.

  11. Highly robust transparent and conductive gas diffusion barriers based on tin oxide.

    PubMed

    Behrendt, Andreas; Friedenberger, Christian; Gahlmann, Tobias; Trost, Sara; Becker, Tim; Zilberberg, Kirill; Polywka, Andreas; Görrn, Patrick; Riedl, Thomas

    2015-10-21

    Transparent and electrically conductive gas diffusion barriers are reported. Tin oxide (SnOx ) thin films grown by atomic layer deposition afford extremely low water vapor transmission rates (WVTR) on the order of 10(-6) g (m(2) day)(-1) , six orders of magnitude better than that established with ITO layers. The electrical conductivity of SnOx remains high under damp heat conditions (85 °C/85% relative humidity (RH)), while that of ZnO quickly degrades by more than five orders of magnitude. PMID:26310881

  12. Influence of thermally-oxidized vegetable oils and animal fats on intestinal barrier function and immune variables in young pigs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To evaluate the effect of feeding thermally-oxidized lipids on metabolic oxidative status, gut barrier function, and immune response of young pigs, 108 barrows (6.67 ± 0.03 kg BW) were assigned to 12 dietary treatments in a 4 × 3 factorial design in addition to a corn-soybean meal control diet. Main...

  13. Characterization of Aluminum Oxide Tunnel Barrier for use in a Non-Local Spin Detection Device

    NASA Astrophysics Data System (ADS)

    Abel, Joseph; Garramone, John; Sitnitsky, Ilona; Labella, Vincent

    2010-03-01

    Aluminum oxide can be utilized as an interface layer between ferromagnetic metals and silicon to achieve spin injection into silicon. The goal of our research is to inject and readout spins using a non-local measurement device that utilizes 1-2 nm aluminum oxide interface layers as tunnel barriers. An important step of fabricating a non-local measurement device out of silicon is the growth of an aluminum oxide tunnel barrierfootnotetextO. van't Erve, A. Hanbicki, M. Holub, C. Li, C. Awo-Affouda, P. Thompson and B. Jonker, Appl. Phys. Lett. 91, 212109 (2007).. Aluminum Oxide thin films where grown using a Knudsen cell to deposit 1 nm, 2 nm, and 3 nm of aluminum. The films were then oxidized in O2. X-ray photoelectron spectroscopy (XPS) was performed to characterize the film stoichiometry, and the band gap. We will also report on current voltage measurements of these films after they have been capped with metal and compare the resistance area product to those calculated for spin injection into siliconfootnotetextB.-C. Min, K. Motohashi, C. Lodder, and R. Jansen, Nat. Mater. 5, 817 (2006). .

  14. Tunneling Characteristics Depending on Schottky Barriers and Diffusion Current in SiOC.

    PubMed

    Oh, Teresa; Kim, Chy Hyung

    2016-02-01

    To obtain a diffusion current in SiOC, the aluminum doped zinc oxide films were deposited on SiOC/Si wafer by a RF magnetron sputtering. All the X-ray patterns of the SiOC films showed amorphous phases. The level of binding energy of Si atoms will lead to an additional potential modulation by long range Coulombic and covalent interactions with oxygen ions. The growth of the AZO film was affected by the characteristics of SiOC, resulting in similar trends in XPS spectra and a shift to higher AZO lattice d values than the original AZO d values in XRD analyses. The charges trapped by the defects at the interlayer between AZO and SiOC films induced the decreased mobility of carriers. In the absence of trap charges, AZO grown on SiOC film such as the sample prepared at O2 = 25 or 30 sccm, which has low charge carrier concentration and high mobility, showed high mobility in an ambipolar characteristic of oxide semiconductor due to the tunneling effect and diffusion current. The structural matching of an interface between AZO and amorphous SiOC enhanced the height of Schottky Barrier (SB), and then the mobility was increased by the tunneling effect from band to band through the high SB. PMID:27433737

  15. Temperature dependence of the Tafel slope and electrochemical barrier symmetry factor,. beta. , in electrode kinetics

    SciTech Connect

    Conway, B.E. ); Tessier, D.F. ); Wilkinson, D.P. )

    1989-09-01

    The significance of the new-established situation that the Tafel slopes, b, ( = d{eta}/d In i) for simple charge-transfer processes at electrodes are usually not represented with respect to variation with temperature, T, by the conventional relation b = RT/{beta} cpF, where {beta} is a constant-valued electrochemical charge-transfer barrier-symmetry coefficient, is examined in the light of recent comments on the problem. Clear evidence is given that b has the form b = RT({beta}sub H + T{beta}{sub s})F for proton transfer at Hg in water and various other solvents, where {beta}{sub H} and T{beta}{sub s} are enthalpic components of the overall {beta}, corresponding to experimentally observable potential-dependence of both the enthalpy and the entropy of activation, respectively. The frequent deviation from conventional behavior thus arises because the entropy of activation, as well as the energy of activation, can be potential-dependent, a situation that, until recently, has been neglected in inter-pretations of electrode-kinetic experiments. The origin of the conventional effect of potential on electrode reaction rates, through the change of electrode work function,{Phi}, with overpotential or electrode potential, V, ({Phi}{sub v} = {Phi}{sub v = O}{plus minus} eV), is examined critically in relation to the potential-dependent surface-potential component, {chi}{sub d}, in {Phi}, which can also be T-dependent.

  16. 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. PMID:26941816

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

    PubMed Central

    Ajami, Sima; Mellat-Karkevandi, Zahra

    2015-01-01

    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. PMID:26941816

  18. The application of the barrier-type anodic oxidation method to thickness testing of aluminum films.

    PubMed

    Chen, Jianwen; Yao, Manwen; Xiao, Ruihua; Yang, Pengfei; Hu, Baofu; Yao, Xi

    2014-09-01

    The thickness of the active metal oxide film formed from a barrier-type anodizing process is directly proportional to its formation voltage. The thickness of the consumed portion of the metal film is also corresponding to the formation voltage. This principle can be applied to the thickness test of the metal films. If the metal film is growing on a dielectric substrate, when the metal film is exhausted in an anodizing process, because of the high electrical resistance of the formed oxide film, a sudden increase of the recorded voltage during the anodizing process would occur. Then, the thickness of the metal film can be determined from this voltage. As an example, aluminum films are tested and discussed in this work. This method is quite simple and is easy to perform with high precision. PMID:25273741

  19. The application of the barrier-type anodic oxidation method to thickness testing of aluminum films

    NASA Astrophysics Data System (ADS)

    Chen, Jianwen; Yao, Manwen; Xiao, Ruihua; Yang, Pengfei; Hu, Baofu; Yao, Xi

    2014-09-01

    The thickness of the active metal oxide film formed from a barrier-type anodizing process is directly proportional to its formation voltage. The thickness of the consumed portion of the metal film is also corresponding to the formation voltage. This principle can be applied to the thickness test of the metal films. If the metal film is growing on a dielectric substrate, when the metal film is exhausted in an anodizing process, because of the high electrical resistance of the formed oxide film, a sudden increase of the recorded voltage during the anodizing process would occur. Then, the thickness of the metal film can be determined from this voltage. As an example, aluminum films are tested and discussed in this work. This method is quite simple and is easy to perform with high precision.

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

    PubMed

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

    2016-05-19

    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. PMID:27168418

  1. 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.

  2. Barrier dependent electron tunneling lifetime in one-dimensional device structures

    NASA Astrophysics Data System (ADS)

    Li, Hui; Gong, Jian; Hu, Xing; Zhang, Rui-Qin

    2010-11-01

    The tunneling times of electrons in one-dimensional potential structures were studied using a projected Green function (PGF) method. The approach was applied to cases with potentials with one barrier, two barriers, and three barriers at the right side of a quantum well where the electron is located at the initial time. Our results include the effects of well width and barrier thickness on the tunneling time, and also show the impact on the tunneling time of splitting a single barrier into more barriers. This study confirms not only the validity of the PGF method but also reveals the impact of the potential structure on the operation speed of resonant tunneling devices.

  3. Role of interfacial oxide in high-efficiency graphene-silicon Schottky barrier solar cells.

    PubMed

    Song, Yi; Li, Xinming; Mackin, Charles; Zhang, Xu; Fang, Wenjing; Palacios, Tomás; Zhu, Hongwei; Kong, Jing

    2015-03-11

    The advent of chemical vapor deposition (CVD) grown graphene has allowed researchers to investigate large area graphene/n-silicon Schottky barrier solar cells. Using chemically doped graphene, efficiencies of nearly 10% can be achieved for devices without antireflective coatings. However, many devices reported in past literature often exhibit a distinctive s-shaped kink in the measured I/V curves under illumination resulting in poor fill factor. This behavior is especially prevalent for devices with pristine (not chemically doped) graphene but can be seen in some cases for doped graphene as well. In this work, we show that the native oxide on the silicon presents a transport barrier for photogenerated holes and causes recombination current, which is responsible for causing the kink. We experimentally verify our hypothesis and propose a simple semiconductor physics model that qualitatively captures the effect. Furthermore, we offer an additional optimization to graphene/n-silicon devices: by choosing the optimal oxide thickness, we can increase the efficiency of our devices to 12.4% after chemical doping and to a new record of 15.6% after applying an antireflective coating. PMID:25685934

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Isothermal Oxidation Behavior of Supersonic Atmospheric Plasma-Sprayed Thermal Barrier Coating System

    NASA Astrophysics Data System (ADS)

    Bai, Yu; Ding, Chunhua; Li, Hongqiang; Han, Zhihai; Ding, Bingjun; Wang, Tiejun; Yu, Lie

    2013-10-01

    In this work, Y2O3 stabilized zirconia-based thermal barrier coatings (TBCs) were deposited by conventional atmospheric plasma spraying (APS) and high efficiency supersonic atmospheric plasma spraying (SAPS), respectively. The effect of Al2O3 layer stability on the isothermal growth behavior of thermally grown oxides (TGOs) was studied. The results revealed that the Al2O3 layer experienced a three-stage change process, i.e., (1) instantaneous growth stage, (2) steady-state growth stage, and (3) depletion stage. The thickness of Al2O3 scale was proved to be an important factor for the growth rate of TGOs. The SAPS-TBCs exhibited a higher Al2O3 stability and better oxidation resistance as compared with the APS-TBCs. Additionally, it was found that inner oxides, especially nucleated on the top of the crest, continually grew and swallowed the previously formed Al2O3 layer, leading to the granulation and disappearance of continuous Al2O3 scale, which was finally replaced by the mixed oxides and spinel.

  6. Simultaneous Remediation of NOx and Oxidation of Soot Using Dielectric Barrier Discharges

    NASA Astrophysics Data System (ADS)

    Dorai, Rajesh; Kushner, Mark J.; Hassouni, Khaled

    2000-10-01

    Plasma remediation of atmospheric pressure gases is being investigated as a means to remove nitrogen oxides (NO_x) from automobilie exhaust. In actual exhausts, unburned hydrocarbons (UHCs) and soot are unavoidably present which impacts the plasma chemistry of NOx removal. In this regard, the feasibility of using a dielectric barrier discharge to simultaneously oxidize soot particles and remove NOx from simulated exhausts has been computationally investigated. The model system is a mixture of N_2/O_2/CO_2/H_2O with ppm levels of CO, H_2, NO, C_3H_6, C_3H8 and soot particles. The model is a global kinetics simulation modified to account for diffusive transport to and from the soot and reactions on the soot surface. Charging of soot due to electrons and ions is also included. Significant changes in gas-phase NOx chemistry occur when including surface reactions due to reduction of NO2 and deactivation of oxidizing radicals generated from the UHCs. Oxidation of the soot particles produces significant increases in CO.

  7. 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.

  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. 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

    2016-02-01

    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. PMID:26732185

  10. Tirandamycin biosynthesis is mediated by co-dependent oxidative enzymes

    NASA Astrophysics Data System (ADS)

    Carlson, Jacob C.; Li, Shengying; Gunatilleke, Shamila S.; Anzai, Yojiro; Burr, Douglas A.; Podust, Larissa M.; Sherman, David H.

    2011-08-01

    Elucidation of natural product biosynthetic pathways provides important insights into the assembly of potent bioactive molecules, and expands access to unique enzymes able to selectively modify complex substrates. Here, we show full reconstitution, in vitro, of an unusual multi-step oxidative cascade for post-assembly-line tailoring of tirandamycin antibiotics. This pathway involves a remarkably versatile and iterative cytochrome P450 monooxygenase (TamI) and a flavin adenine dinucleotide-dependent oxidase (TamL), which act co-dependently through the repeated exchange of substrates. TamI hydroxylates tirandamycin C (TirC) to generate tirandamycin E (TirE), a previously unidentified tirandamycin intermediate. TirE is subsequently oxidized by TamL, giving rise to the ketone of tirandamycin D (TirD), after which a unique exchange back to TamI enables successive epoxidation and hydroxylation to afford, respectively, the final products tirandamycin A (TirA) and tirandamycin B (TirB). Ligand-free, substrate- and product-bound crystal structures of bicovalently flavinylated TamL oxidase reveal a likely mechanism for the C10 oxidation of TirE.

  11. 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.

  12. The tunneling solutions of the time-dependent Schroedinger equation for a square-potential barrier

    SciTech Connect

    Elci, A.; Hjalmarson, H. P.

    2009-10-15

    The exact tunneling solutions of the time-dependent Schroedinger equation with a square-potential barrier are derived using the continuous symmetry group G{sub S} for the partial differential equation. The infinitesimal generators and the elements for G{sub S} are represented and derived in the jet space. There exist six classes of wave functions. The representative (canonical) wave functions for the classes are labeled by the eigenvalue sets, whose elements arise partially from the reducibility of a Lie subgroup G{sub LS} of G{sub S} and partially from the separation of variables. Each eigenvalue set provides two or more time scales for the wave function. The ratio of two time scales can act as the duration of an intrinsic clock for the particle motion. The exact solutions of the time-dependent Schroedinger equation presented here can produce tunneling currents that are orders of magnitude larger than those produced by the energy eigenfunctions. The exact solutions show that tunneling current can be quantized under appropriate boundary conditions and tunneling probability can be affected by a transverse acceleration.

  13. Hypoxia-Inducible Factor 1–Dependent Induction of Intestinal Trefoil Factor Protects Barrier Function during Hypoxia

    PubMed Central

    Furuta, Glenn T.; Turner, Jerrold R.; Taylor, Cormac T.; Hershberg, Robert M.; Comerford, Katrina; Narravula, Sailaja; Podolsky, Daniel K.; Colgan, Sean P.

    2001-01-01

    Mucosal organs such as the intestine are supported by a rich and complex underlying vasculature. For this reason, the intestine, and particularly barrier-protective epithelial cells, are susceptible to damage related to diminished blood flow and concomitant tissue hypoxia. We sought to identify compensatory mechanisms that protect epithelial barrier during episodes of intestinal hypoxia. Initial studies examining T84 colonic epithelial cells revealed that barrier function is uniquely resistant to changes elicited by hypoxia. A search for intestinal-specific, barrier-protective factors revealed that the human intestinal trefoil factor (ITF) gene promoter bears a previously unappreciated binding site for hypoxia-inducible factor (HIF)-1. Hypoxia resulted in parallel induction of ITF mRNA and protein. Electrophoretic mobility shift assay analysis using ITF-specific, HIF-1 consensus motifs resulted in a hypoxia-inducible DNA binding activity, and loading cells with antisense oligonucleotides directed against the α chain of HIF-1 resulted in a loss of ITF hypoxia inducibility. Moreover, addition of anti-ITF antibody resulted in a loss of barrier function in epithelial cells exposed to hypoxia, and the addition of recombinant human ITF to vascular endothelial cells partially protected endothelial cells from hypoxia-elicited barrier disruption. Extensions of these studies in vivo revealed prominent hypoxia-elicited increases in intestinal permeability in ITF null mice. HIF-1–dependent induction of ITF may provide an adaptive link for maintenance of barrier function during hypoxia. PMID:11342587

  14. Permeability of the blood-brain barrier depends on brain temperature

    PubMed Central

    Kiyatkin, Eugene A.; Sharma, Hari S.

    2009-01-01

    Increased permeability of the blood-brain barrier (BBB) has been reported in different conditions accompanied by hyperthermia, but the role of brain temperature per se in modulating brain barrier functions has not been directly examined. To delineate the contribution of this factor, we examined albumin immunoreactivity in several brain structures (cortex, hippocampus, thalamus and hypothalamus) of pentobarbital-anesthetized rats (50 mg/kg, ip), which were passively warmed to different levels of brain temperature (32–42°C). Similar brain structures were also examined for the expression of glial fibrillary acidic protein (GFAP), an index of astrocytic activation, water and ion content, and morphological cell abnormalities. Data were compared with those obtained from drug-free awake rats with normal brain temperatures (36–37°C). The numbers of albumin- and GFAP-positive cells strongly correlates with brain temperature, gradually increasing from ~38.5°C and plateauing at 41–42°C. Brains maintained at hyperthermia also showed larger content of brain water and Na+, K+ and Cl− as well as structural abnormalities of brain cells, all suggesting acute brain edema. The latter alterations were seen at ~39°C, gradually progressed with temperature increase, and peaked at maximum hyperthermia. Temperature-dependent changes in albumin immunoreactivity tightly correlated with GFAP immunoreactivity, brain water, and numbers of abnormal cells; they were found in each tested area, but showed some structural specificity. Notably, a mild BBB leakage, selective glial activation, and specific cellular abnormalities were also found in the hypothalamus and piriform cortex during extreme hypothermia (32–33°C); in contrast to hyperthermia these changes were associated with decreased levels of brain water, Na+ and K+, suggesting acute brain dehydration. Therefore, brain temperature per se is an important factor in regulating BBB permeability, alterations in brain water

  15. 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

    2016-03-01

    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. PMID:26849085

  16. Nitrate-Dependent Ferrous Iron Oxidation by Anaerobic Ammonium Oxidation (Anammox) Bacteria

    PubMed Central

    Oshiki, M.; Ishii, S.; Yoshida, K.; Fujii, N.; Ishiguro, M.; Satoh, H.

    2013-01-01

    We examined nitrate-dependent Fe2+ oxidation mediated by anaerobic ammonium oxidation (anammox) bacteria. Enrichment cultures of “Candidatus Brocadia sinica” anaerobically oxidized Fe2+ and reduced NO3− to nitrogen gas at rates of 3.7 ± 0.2 and 1.3 ± 0.1 (mean ± standard deviation [SD]) nmol mg protein−1 min−1, respectively (37°C and pH 7.3). This nitrate reduction rate is an order of magnitude lower than the anammox activity of “Ca. Brocadia sinica” (10 to 75 nmol NH4+ mg protein−1 min−1). A 15N tracer experiment demonstrated that coupling of nitrate-dependent Fe2+ oxidation and the anammox reaction was responsible for producing nitrogen gas from NO3− by “Ca. Brocadia sinica.” The activities of nitrate-dependent Fe2+ oxidation were dependent on temperature and pH, and the highest activities were seen at temperatures of 30 to 45°C and pHs ranging from 5.9 to 9.8. The mean half-saturation constant for NO3− ± SD of “Ca. Brocadia sinica” was determined to be 51 ± 21 μM. Nitrate-dependent Fe2+ oxidation was further demonstrated by another anammox bacterium, “Candidatus Scalindua sp.,” whose rates of Fe2+ oxidation and NO3− reduction were 4.7 ± 0.59 and 1.45 ± 0.05 nmol mg protein−1 min−1, respectively (20°C and pH 7.3). Co-occurrence of nitrate-dependent Fe2+ oxidation and the anammox reaction decreased the molar ratios of consumed NO2− to consumed NH4+ (ΔNO2−/ΔNH4+) and produced NO3− to consumed NH4+ (ΔNO3−/ΔNH4+). These reactions are preferable to the application of anammox processes for wastewater treatment. PMID:23624480

  17. 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.

  18. 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

  19. 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

    2013-01-01

    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 function

  20. 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.

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

    PubMed

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

    2015-07-10

    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. PMID:26080998

  2. Spinel oxides: 1 spin-filter barrier for a class of magnetic tunnel junctions

    SciTech Connect

    Zhang, J.; Zhang, Xiaoguang; Han, Prof. X. F.

    2012-01-01

    The orbital composition of the electrode wave functions and the complex bands within the barrier band gap are two important factors in deciding the spin-filter effect. This is illustrated in a class of spinel oxides, including MgAl2O4, ZnAl2O4, SiMg2O4, and SiZn2O4. Through first-principles calculations of the complex bands and electron transmission along the [001] direction, they are shown to have the same D1 spin-filter effect as MgO due to the combination of both factors. Due to better lattice match with typical bcc magnetic electrodes than MgO, these materials provide a broad spectrum of candidate materials for magnetic tunnel junctions.

  3. 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.

  4. 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.

  5. 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.

  6. A study on thermal barrier coatings including thermal expansion mismatch and bond coat oxidation

    NASA Technical Reports Server (NTRS)

    Chang, George C.; Phucharoen, Woraphat; Miller, Robert A.

    1986-01-01

    The present investigation deals with a plasma-sprayed thermal barrier coating (TBC) intended for high temperature applications to advanced gas turbine blades. Typically, this type of coating system consists of a zirconia-yttria ceramic layer with a nickel-chromium-aluminum bond coat on a superalloy substrate. The problem on hand is a complex one due to the fact that bond coat oxidation and thermal mismatch occur in the TBC. Cracking in the TBC has also been experimentally illustrated. A clearer understanding of the mechanical behavior of the TBC is investigated. The stress states in a model thermal barrier coating as it cools down in air is studied. The powerful finite element method was utilized to model a coating cylindrical specimen. Four successively refined finite element models were developed. Some results obtained using the first two models have been reported previously. The major accomplishment is the successful development of an elastic TBC finite element model known as TBCG with interface geometry between the ceramic layer and the bond coat. An equally important milestone is the near-completion of the new elastic-plastic TBC finite element model called TBCGEP which yielded initial results. Representative results are presented.

  7. Study of the water barrier properties of polyester paints after photo-oxidative degradation

    SciTech Connect

    Deflorian, F.; Fedrizzi, L.; Bonora, P.L.

    1996-10-01

    The capacitance of an organic coating, applied on a metal substrate for protection against corrosion, can undergo a decrease following some deterioration processes due to the interaction with the environment. In particular, the barrier properties of a paint are strongly influenced, for example, by the presence of defects, by photo-oxidative phenomena and by the adhesive properties of the polymer-metal interface. Impedance spectroscopy is a flexible and efficacious instrument for assessing all these phenomena and is useful in supplying information on the mechanisms of deterioration as well as in assessing the physical parameters associated with it. The scope of this work is to study in detail the photosensitive effects of UV radiation on the water barrier properties of industrially produced polyester organic coating. The coefficients of diffusion and the values of permeability and saturation for different UV radiation intervals, have been calculated, starting from the impedance data and using appropriate models. So the relationship between these values and the effective long term properties of protection from corrosion of the paints was evaluated.

  8. Characteristics of titanium oxide memristor with coexistence of dopant drift and a tunnel barrier

    NASA Astrophysics Data System (ADS)

    Tian, Xiao-Bo; Xu, Hui

    2014-06-01

    The recent published experimental data of titanium oxide memristor devices which are tested under the same experimental conditions exhibit the strange instability and complexity of these devices. Such undesired characteristics preclude the understanding of the device conductive processes and the memristor-based practical applications. The possibility of the coexistence of dopant drift and tunnel barrier conduction in a memristor provides preliminary explanations for the undesired characteristics. However, current research lacks detailed discussion about the coexistence case. In this paper, dopant drift and tunnel barrier-based theories are first analyzed for studying the relations between parameters and physical variables which affect characteristics of memristors, and then the influences of each parameter change on the conductive behaviors in the single and coexistence cases of the two mechanisms are simulated and discussed respectively. The simulation results provide further explanations of the complex device conduction. Theoretical methods of eliminating or reducing the coexistence of the two mechanisms are proposed, in order to increase the stability of the device conduction. This work also provides the support for optimizing the fabrications of memristor devices with excellent performance.

  9. Polymer-graphene oxide quadlayer thin-film assemblies with improved gas barrier.

    PubMed

    Tzeng, Ping; Stevens, Bart; Devlaming, Ian; Grunlan, Jaime C

    2015-06-01

    Layer-by-layer assembly was used to create quadlayers (QLs) of chitosan (CH), poly(acrylic acid) (PAA), CH, and graphene oxide (GO). Electron microscopy confirmed GO coverage over the film and a highly ordered nanobrick wall structure. By varying pH deviation between CH and PAA, a thick and interdiffused polymer matrix was created because of the altered chain conformation. A 5 CH (pH 5.5)/PAA (pH 3)/CH (pH 5.5)/GO QL assembly (48 nm) exhibits very low oxygen permeability (3.9 × 10(-20) cm(3) cm cm(-2) Pa(-1) s(-1)) that matches SiOx barrier coatings. In an effort to maintain barrier performance under high humidity, GO was thermally reduced to increase hydrophobicity of the film. This reduction step increased H2/CO2 selectivity of a 5 QL film from 5 to 215, exceeding Robeson's upper bound limit. This unique water-based multilayer nanocoating is very promising for a variety of gas purification and packaging applications. PMID:25970136

  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. 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. PMID:17451824

  12. Buprenorphine Maintenance for Opioid Dependence in Public Sector Healthcare: Benefits and Barriers

    PubMed Central

    Duncan, Laura G.; Mendoza, Sonia; Hansen, Helena

    2015-01-01

    Background Since its U.S. FDA approval in 2002, buprenorphine has been available for maintenance treatment of opiate dependence in primary care physicians’ offices. Though buprenorphine was intended to facilitate access to treatment, disparities in utilization have emerged; while buprenorphine treatment is widely used in private care setting, public healthcare integration of buprenorphine lags behind. Results Through a review of the literature, we found that U.S. disparities are partly due to a shortage of certified prescribers, concern of patient diversion, as well as economic and institutional barriers. Disparity of buprenorphine treatment dissemination is concerning since buprenorphine treatment has specific characteristics that are especially suited for low-income patient population in public sector healthcare such as flexible dosing schedules, ease of concurrently treating co-morbidities such as HIV and hepatitis C, positive patient attitudes towards treatment, and the potential of reducing addiction treatment stigma. Conclusion As the gap between buprenorphine treatment in public sector settings and private sector settings persists in the U.S., current research suggests ways to facilitate its dissemination. PMID:27088135

  13. Anomalous Fano resonance of massive Dirac particle through a time-dependent barrier

    NASA Astrophysics Data System (ADS)

    Zhang, Cunxi; Liu, Jie; Fu, Libin

    2015-06-01

    As is well known Fano resonance arises from the interference between a localized state and a continuum state. Using the standard Floquet theory and the scattering matrix method, we study theoretically the massive Dirac particle transmission over a quantum barrier with an oscillating field. It is found that the massive relativistic particles can generate not only normal Fano resonance in the transmission due to the interference between a localized state (bound state) and the continuum state, but also anomalous Fano resonance due to the interference between a delocalized state (extended state) and the continuum state. The dependence of line shapes on driving parameters for these two kinds of Fano resonances is quite different. For normal Fano resonance the asymmetry parameter is approximately proportional to a power law of the amplitude of the oscillating field, while for the anomalous Fano resonance the asymmetry parameters change slightly with different oscillation amplitudes. In practice, the anomalous Fano resonance can be identified by observing asymmetry parameters in experiment.

  14. AIDS and chemical dependency: special issues and treatment barriers for gay and bisexual men.

    PubMed

    Cabaj, R P

    1989-01-01

    Because gay and bisexual men continue to be the largest at-risk group for human immunodeficiency virus (HIV) related conditions, the special role of substance abuse, and not just intravenous drug abuse, must be understood in order to provide adequate services and prevention. Gay men and women appear to have a higher incidence of substance abuse than the general population. Genetic, biochemical, societal, and cultural factors may all contribute to this increase, especially the overwhelming impact of societal homophobia. To address the treatment barriers to gay and bisexual men seeking or needing treatment for HIV-related conditions, chemical dependence or both, the gay community should be seen like any other minority community. The social and cultural norms of this widely varied community should be studied: the socialization of being gay in mainstream society, including the awareness of being different; the coming-out process; and dealing with internalized homophobia need to be understood. In addition, the resistance or anxiety health care providers may feel in working with gay or bisexual men or with HIV-related conditions should be addressed. PMID:2621509

  15. TLR4 induces CCR7-dependent monocytes transmigration through the blood-brain barrier.

    PubMed

    Paradis, Alexandre; Bernier, Stéphane; Dumais, Nancy

    2016-06-15

    In this study, we examined whether bacterial pathogen-associated molecular patterns recognized by toll-like receptors (TLRs) can modify the CCR7-dependent migration of human monocytes. MonoMac-1 (MM-1) cells and freshly isolated human monocytes were cultivated in the presence of agonists for TLR4 (which senses lipopolysaccharides from gram-negative bacteria), TLR1/2 (which senses peptidoglycan from gram-positive bacteria), and TLR9 (which recognizes bacterial DNA rich in unmethylated CpG DNA). CCR7 mRNA transcription was measured using quantitative reverse transcription polymerase chain reaction and protein expression was examined using flow cytometry. CCR7 function was monitored using migration and transmigration assays in response to CCL19/CCL21, which are natural ligands for CCR7. Our results show that TLR4 strongly increases monocyte migratory capacity in response to CCL19 in chemotaxis and transmigration assays in a model that mimics the human blood-brain barrier, whereas TLR1/2 and 9 have no effect. Examination of monocyte migration in response to TLRs that are activated by bacterial components would contribute to understanding the excessive monocyte migration that characterizes the pathogenesis of bacterial infections and/or neuroinflammatory diseases. PMID:27235343

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

    SciTech Connect

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

    2014-03-28

    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 SiO{sub 2} thickness and using comb-shaped electrodes with smaller tooth spacing. Meantime, the high and steady photosensitivity can also be approached by introducing HfO{sub 2} into dielectric stacks.

  17. The oxidative activities of membrane vesicles from Bacillus caldolyticus. Energy-dependence of succinate oxidation.

    PubMed

    Dawson, A G; Chappell, J B

    1978-02-15

    1. The properties of membrane vesicles from the extreme thermophile Bacillus caldolyticus were investigated. 2. Vesicles prepared by exposure of spheroplasts to ultrasound contained cytochromes a, b and c, and at 50 degrees C they rapidly oxidized NADH and ascorbate in the presence of tetramethyl-p-phenylenediamine. Succinate and l-malate were oxidized more slowly, and dl-lactate, l-alanine and glycerol 1-phosphate were not oxidized. 3. In the absence of proton-conducting uncouplers the oxidation of NADH was accompanied by a net translocation of H(+) into the vesicles. Hydrolysis of ATP by a dicyclohexylcarbodi-imide-sensitive adenosine triphosphatase was accompanied by a similarly directed net translocation of H(+). 4. Uncouplers (carbonyl cyanide p-trifluoromethoxyphenylhydrazone or valinomycin plus NH(4) (+)) prevented net H(+) translocation but stimulated ATP hydrolysis, NADH oxidation and ascorbate oxidation. The last result suggested an energy-conserving site in the respiratory chain between cytochrome c and oxygen. 5. Under anaerobic conditions the reduction of cytochrome b by ascorbate (with tetramethyl-p-phenylenediamine) was stimulated by ATP hydrolysis, indicating an energy-conserving site between cytochrome b and cytochrome c. However, no reduction of NAD(+) supported by oxidation of succinate, malate or ascorbate occurred, neither did it with these substrates in the presence of ATP under anaerobic conditions, suggesting that there was no energy-conserving site between NADH and cytochrome b. 6. Succinate oxidation, in contrast with that of NADH and ascorbate, was strongly inhibited by uncouplers and stimulated by ATP hydrolysis. These effects were not observed when phenazine methosulphate, which transfers electrons from succinate dehydrogenase directly to oxygen, was present. It was concluded that in these vesicles the oxidation of succinate was energy-dependent and that the reoxidation of reduced succinate dehydrogenase was dependent on the outward

  18. Correlation between nicotine dependence and barriers to cessation between exclusive cigarette smokers and dual (water pipe) smokers among Arab Americans

    PubMed Central

    El-Shahawy, Omar; Haddad, Linda

    2015-01-01

    Background Evidence suggests that dual cigarette and water pipe use is growing among minority groups, particularly among Arab Americans. Differences in nicotine dependence and barriers to smoking cessation among such dual smokers have not been previously examined in this population. We examined potential differences that might exist between exclusive cigarette smokers and dual smokers (cigarette and water pipe) pertaining to nicotine dependence and barriers to cessation among Arab Americans. Methods We conducted a cross-sectional study using a convenience sample of self-identified Arab immigrant smokers (n=131) living in the Richmond, VA metropolitan area. Data were collected using four questionnaires: Demographic and Cultural Information questionnaire, Tobacco Use questionnaire, Fagerström Test for Nicotine Dependence (FTND) questionnaire, and Barriers to Cessation questionnaire. We examined differences in nicotine dependence and barriers to cessation between exclusive cigarette smokers and dual smokers of cigarettes and water pipe. Furthermore, we explored the correlations of these measures with select variables. Results There was a significant difference in the FTND scores between the exclusive cigarette smokers (mean M=2.55, standard deviation [SD] =2.10) and dual smokers (M=3.71, SD =2.42); t(129) = (2.51), P=0.0066. There was also a significant difference in the Barriers to Cessation scores between exclusive cigarette smokers (M=38.47, SD =13.07) and dual smokers (M=45.21, SD =9.27); t(129) = (2.56), P=0.0058. Furthermore, there was a highly significant correlation among FTND scores, Barriers to Cessation scores, and past quit attempts among dual smokers. Conclusion Water pipe tobacco smoking seems to be both adding to the dependence potential of cigarette smoking and enhancing barriers to cessation in our study sample. However, the high correlation between quit attempts, FTND, and barriers to cessation needs further investigation to ascertain the possible

  19. Tritium permeation barrier-aluminized coating prepared by Al-plating and subsequent oxidation process

    NASA Astrophysics Data System (ADS)

    Guikai, Zhang; Ju, Li; Chang'an, Chen; Sanping, Dou; Guoping, Ling

    2011-10-01

    Aluminum rich coatings forming Al 2O 3 on surface are widely applied as tritium permeation barrier (TPB) on structural materials in fusion reactor. In this work, we proposed a new three-step method for preparing such aluminum rich coating on HR-2 steel: ambient temperature melts salt electroplating followed by heat treating and artificial oxidation at 700 °C. Al deposition from AlCl 3/EMIC was performed with a deposition rate of 15 μm/h. After heat treated for 2 h, the aluminized coating appeared homogeneous, with thickness of 11-13 μm and free of visible porosity, and exhibited a three-layer structure. After oxidized in 10 -2 Pa O 2 for 80 h, the finally fabricated coating showed a double-layered structure consisting of an outer γ-A1 2O 3 layer with thickness of 0.1 μm and inner (Fe,Cr,Mn,Ni)Al/(Fe,Cr,Mn,Ni) 3Al layer of 32 μm thickness, without any visible defects. The deuterium permeation rate through the coated HR-2 steel was reduced by 2-3 orders of magnitude at 600-727 °C.

  20. Anandamide rescues retinal barrier properties in Müller glia through nitric oxide regulation.

    PubMed

    Krishnan, G; Chatterjee, N

    2015-01-22

    The blood retinal barrier (BRB) can mitigate deleterious immune response. Dysfunction at the BRB can affect disease progression. Under inflammatory conditions Müller glia produce increased pro-inflammatory factors, like nitric oxide (NO). In this study we describe molecular events at the Müller glia during inflammation which could affect inner BRB properties. Griess assay and 4,5-diaminofluorescein diacetate (DAF-2DA) time-lapse fluorescence were used to measure NO production. Western blot was used to analyze the expression of inducible nitric oxide synthase (iNOS) and mitogen-activated protein kinases (MAPK) components. Lucifer Yellow was used to measure permeability. Griess assay and DAF-2DA time-lapse fluorescence images revealed that lipopolysaccharide (LPS) induced inflammation and increased NO production. In parallel, changes were observed in tight junction proteins, zona occludens 1 (ZO-1), connexin 43 (Cx43), and permeability. This was mediated through activation of iNOS and mitogen-activated protein kinase phosphatase-1 (MKP-1), implicated in immune response. Endocannabinoids can exert a protective and anti-inflammatory effect. Exogenous arachidonoyl ethanolamide (AEA) inhibited NO generation and also abolished LPS-induced increase in permeability. Our work suggests that subtle changes in Müller glia function, which act as part of the BRB, could contribute to retinal health. AEA which can reduce inflammatory cytotoxicity has potential as treatment in several ocular manifestations where the integrity of the BRB is crucial. PMID:25453774

  1. Oxidation Behavior of Thermal Barrier Coatings with a TiAl3 Bond Coat on γ-TiAl Alloy

    NASA Astrophysics Data System (ADS)

    Wang, Jiqiang; Kong, Lingyan; Li, Tiefan; Xiong, Tianying

    2015-02-01

    The thermal barrier coatings investigated in this paper included a TiAl3 bond coat and a yttria partially stabilized zirconia (YSZ) layer. The TiAl3 bond coat was prepared by deposition of aluminum by cold spray, followed by a heat-treatment. The YSZ layer was prepared by air plasma spray. The isothermal and cyclic oxidation tests were conducted at 900 °C for 1000 h and 500 cycles to test the oxidation resistance of the thermal barrier coatings. The microstructure and composition of the γ-TiAl alloy with and without the thermal barrier coatings after oxidation were investigated. The results showed that a dense TGO layer about 5 μm had grown between the YSZ layer and the TiAl3 bond coat. The TGO had good adhesion to both the YSZ layer and the bond coat even after the TiAl3 bond coat entirely degraded into the TiAl2 phase, which decreased the inward oxygen diffusion. Thus, the thermal barrier coatings improved the oxidation resistance of γ-TiAl alloy effectively.

  2. Nitronyl nitroxides, a novel group of protective agents against oxidative stress in endothelial cells forming the blood-brain barrier.

    PubMed

    Blasig, I E; Mertsch, K; Haseloff, R F

    2002-11-01

    Nitronyl nitroxides (NN) effectively decompose free radicals (. As brain endothelium, forming the blood-brain barrier (BBB), is both the main source and the target of reactive species during cerebral oxidative stress, we studied the effect of NN on brain endothelial cells injured by the mediator of oxidative stress H(2)O(2) (. H(2)O(2) caused hydroxyl radical generation, lipid peroxidation, membrane dysfunction, membrane leak and cell death, concentration dependently. Due to 0.5 mM H(2)O(2), oxy-radical-induced membrane phospholipid peroxidation (malondialdehyde) increased to 0.61+/-0.04 nmol/mg protein vs control (0.32+/-0.03, p<0.05), cells lost cytosolic proteins into the medium and viability decreased to 28+/-2% of control (p<0.05). Permeability through the endothelial monolayer (measure for the tightness of the BBB) rose to 250+/-40% after 0.15 mM H(2)O(2) (p<0.001). Addition of 10 microM of the NN 5,5-dimethyl-2,4-diphenyl-4-methoxy-2-imidazoline-3-oxide-1-oxyl (NN-2), 1 mM phenylbutyl nitrone (PBN), or 10 microM of the lazaroid U83836E improved cell viability during incubation with 0.5 mM H(2)O(2) to 57+/-1%, 49+/-2%, and 42+/-3% (p<0.05, vs drug-free H(2)O(2) group). The permeability enhancement by 0.15 mM H(2)O(2) was reduced to 171+/-21%, 170+/-25%, and 118+/-32% (p<0.05 vs drug-free H(2)O(2) group). Generally, the assumption is supported that during cerebral oxidative stress the protection should also be directed to the cells of the BBB, which can be provided by antioxidative approaches. NN represent a new group of antioxdatively acting cytoprotectiva improving the survival and function of the endothelium against oxidative stress. PMID:12423670

  3. Improved Oxidation Life of Segmented Plasma Sprayed 8YSZ Thermal Barrier Coatings

    NASA Astrophysics Data System (ADS)

    Smialek, James L.

    2004-03-01

    Unconventional plasma sprayed thermal barrier coating (TBC) systems were produced and evaluated by interrupted or cyclic furnace oxidation life testing. First, approximately 250 µm thick 8YSZ coatings were directly sprayed onto grit blasted surfaces of PWA 1484, without a bond coat, to take advantage of the excellent oxidation resistance of this superalloy. For nominal sulfur (S) contents of 1 ppmw, total coating separation took place at relatively short times (200 h at 1100°C). Reductions in the S content, by melt desulfurization commercially (0.3 ppmw) or by hydrogen (H2) annealing in the laboratory (0.01 ppmw), improved scale adhesion and extended life appreciably, by factors of 5-10. However, edge-initiated failure persisted, producing massive delamination as one sheet of coating. Secondly, surfaces of melt desulfurized PWA 1484 were machined with a grid of grooves or ribs (˜250 µm wide and high), resulting in a segmented TBC surface macrostructure, for the purpose of subverting this failure mechanism. In this case, failure occurred only as independent, single-segment events. For grooved samples, 1100 °C segment life was extended to ˜1000h for 5 mm wide segments, with no failure observed out to 2000 h for segments ≤2.5 mm wide. Ribbed samples were even more durable, and segments ≤6 mm remained intact for 2000 h. Larger segments failed by buckling at times inversely related to the segment width and decreased by oxidation effects at higher temperatures. This critical buckling size was consistent with that predicted for elastic buckling of a TBC plate subject to thermal expansion mismatch stresses. Thus, low S substrates demonstrate appreciable coating lives without a bond coat, while rib segmenting extends life considerably.

  4. Microbubble Type and Distribution Dependence of Focused Ultrasound Induced Blood Brain Barrier Opening

    PubMed Central

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

    2014-01-01

    Focused Ultrasound (FUS) in the presence of microbubbles has been used to non-invasively induce reversible blood brain barrier (BBB) opening in both rodents and non-human primates. This study aims at identifying the dependence of the BBB opening properties on the polydisperse microbubble (since all clinically approved microbubbles are polydisperse) type and distribution by using clinically approved UCA (Definity®) and in-house made polydisperse microbubbles (IHP) in mice. A total of 18 C57BL/6 mice (n = 3) were used in this study, and each mouse received either Definity® or IHP microbubbles via tail vein injection. The concentration and size distribution of both the activated Definity® and IHP microbubbles were measured and diluted to 6×108/ml prior to injection. Immediately after the microbubble administration, FUS sonications were carried out with the following parameters: frequency of 1.5 MHz, pulse repetition frequency of 10 Hz, 1000 cycles, in situ peak rarefactional acoustic pressures of 0.3 MPa, 0.45 MPa, and 0.6 MPa for a sonication duration of 60 s. Contrast-enhanced magnetic resonance imaging (MRI) was used to confirm the BBB opening and allowed for image-based analysis. The permeability of the treated region and volumes of BBB opening using the two types of microbubbles did not show significant difference (P > 0.05) for PRPs of 0.45 MPa and 0.6 MPa, while IHP microbubbles showed significantly higher permeability and volume of opening (P < 0.05) at the relatively lower pressure of 0.3 MPa. The results from this study indicate that the microbubble type and distribution could have significant effects on the FUS-induced BBB opening at lower, but less important at higher, pressure levels, possibly due to the stable cavitation that governs the former. This difference may have become less significant at higher FUS pressure levels where inertial cavitation typically occurs. PMID:24239362

  5. 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

  6. Ursodeoxycholic acid ameliorates experimental ileitis counteracting intestinal barrier dysfunction and oxidative stress.

    PubMed

    Bernardes-Silva, Carlos Felipe; Damião, Adérson O M C; Sipahi, Aytan M; Laurindo, Francisco R M; Iriya, Kiyoshi; Lopasso, Fabio P; Buchpiguel, Carlos A; Lordello, Maria Laura L; Agostinho, Carmem L O; Laudanna, Antonio A

    2004-10-01

    The aim of this study was to evaluate the effect of ursodeoxycholic acid (UDCA) on intestinal permeability (IP) and reactive oxygen species (ROS) generation in indomethacin-induced enteropathy, a well-known experimental model of Crohn's disease. Seventy-eight male Wistar rats were randomly assigned to receive indomethacin, indomethacin + UDCA, or vehicles. Indomethacin induced a significant increase in the fraction of urinary excretion of 51Cr-EDTA following oral administration (7.9 +/- 1.3 vs 2.3 +/- 0.2%; P < 0.05) and lucigenin-amplified chemiluminescence in intestinal fragments ex vivo (10.1 +/- 1.9 vs 2.6 +/- 0.4 cpm x 10(3)/mg; P < 0.05) compared to controls. UDCA significantly reversed these effects (P < 0.05), without being incorporated in biliary bile acid composition (HPLC analysis). These findings support a local protective effect of UDCA in experimental ileitis by the modulation of intestinal barrier dysfunction and oxidative stress. In short, they provide insights into mechanisms of action of UDCA in intestinal inflammation and a new perspective on the treatment of Crohn's disease. PMID:15573906

  7. 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

  8. 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.

  9. Blood-brain barrier properties in vitro depend on composition and assembly of endogenous extracellular matrices.

    PubMed

    Zobel, Kathrin; Hansen, Uwe; Galla, Hans-Joachim

    2016-08-01

    Brain capillary endothelial cells, which constitute the blood-brain barrier (BBB), are enveloped by the extracellular matrix (ECM) produced by endothelial cells, pericytes and astrocytes. The contribution of matrix components secreted by the various cell types at the neurovascular unit, however, remains unclear with respect to their effect on endothelial barrier function. In this study, a new in vitro model was established by growing endothelial cells on an ECM produced by pericytes, astrocytes or a serial combination of both. The last-mentioned was found to be more in vivo-like. We investigated the role of the composition and morphology of ECM supra-structures in maintaining BBB function. The composition was analysed by protein analysis (enzyme-linked immunosorbent assay) and the ultrastructure of generated matrices was analysed by transmission electron microscopy including immunogold labelling. We could show by electric cell-substrate impedance sensing measurements that pericytes and combined matrices significantly improved the barrier tightness of porcine brain capillary endothelial cells (PBCEC). The increase of the resistance was verified by enhanced expression of tight junction proteins. Thus, for the first time, we have shown that barrier integrity is strictly controlled by the ECM, which is a product of all cells involved in the secretion of ECM components and their modification by corresponding cells. Moreover, we have demonstrated that complex matrices by the various cells of the BBB induce barrier marker enzymes in PBCEC, such as alkaline phosphatase. PMID:27053246

  10. Pentylentetrazole-induced loss of blood-brain barrier integrity involves excess nitric oxide generation by neuronal nitric oxide synthase.

    PubMed

    Danjo, Sonoko; Ishihara, Yasuhiro; Watanabe, Masatomo; Nakamura, Yu; Itoh, Kouichi

    2013-09-12

    Dysfunction of the blood-brain barrier (BBB) is one of the major pathophysiological consequences of epilepsy. The increase in the permeability caused by BBB failure is thought to contribute to the development of epileptic outcomes. We developed a method by which the BBB permeability can be demonstrated by gadolinium-enhanced T1 weighted imaging (GdET1WI). The present study examined the changes in the BBB permeability in mice with generalized convulsive seizures (GCS) induced by acute pentylentetrazole (PTZ) injection. At 15min after PTZ-induced GCS, the BBB temporarily leaks BBB-impermeable contrast agent into the parenchyma of the diencephalon, hippocampus and cerebral cortex in mice, and the loss of BBB integrity was gradually recovered by 24h. The temporary BBB failure is a critical link to the glutamatergic activities that occur following the injection of PTZ. PTZ activates the glutamatergic pathway via the NMDA receptor, then nitric oxide (NO) is generated by NMDA receptor-coupled neuronal NO synthase (nNOS). To examine the influence of nNOS-derived NO induced by PTZ on the increases of the BBB permeability, GdET1WI was performed using conventional nNOS gene-deficient mice with or without PTZ injection. The failure of the BBB induced by PTZ was completely protected by nNOS deficiency in the brain. These results suggest that nNOS-derived excess NO in the glutamatergic pathway plays a key role in the failure of the BBB during PTZ-induced GCS. The levels of NO synthetized by nNOS in the brain may represent an important target for the future development of drugs to protect the BBB. PMID:23831997

  11. Electrical spin injection and detection in silicon nanowires through oxide tunnel barriers.

    PubMed

    Zhang, Shixiong; Dayeh, Shadi A; Li, Yan; Crooker, Scott A; Smith, Darryl L; Picraux, S T

    2013-02-13

    We demonstrate all-electrical spin injection, transport, and detection in heavily n-type-doped Si nanowires using ferromagnetic Co/Al(2)O(3) tunnel barrier contacts. Analysis of both local and nonlocal spin valve signals at 4 K on the same nanowire device using a standard spin-transport model suggests that high spin injection efficiency (up to ~30%) and long spin diffusion lengths (up to ~6 μm) are achieved. These values exceed those reported for spin transport devices based on comparably doped bulk Si. The spin valve signals are found to be strongly bias and temperature dependent and can invert sign with changes in the dc bias current. The influence of the nanowire morphology on field-dependent switching of the contacts is also discussed. Owing to their nanoscale geometry, ~5 orders of magnitude less current is required to achieve nonlocal spin valve voltages comparable to those attained in planar microscale spin transport devices, suggesting lower power consumption and the potential for applications of Si nanowires in nanospintronics. PMID:23324028

  12. Spin injection and detection in a graphene lateral spin valve using an yttrium-oxide tunneling barrier

    NASA Astrophysics Data System (ADS)

    Komatsu, Katsuyoshi; Kasai, Shinya; Li, Song-Lin; Nakaharai, Shu; Mitoma, Nobuhiko; Yamamoto, Mahito; Tsukagoshi, Kazuhito

    2014-08-01

    We demonstrate charge and spin current transport in a graphene-based lateral spin valve using yttrium oxide (Y-O) as a tunneling barrier between graphene and a ferromagnetic electrode. A Y-O layer grown on graphene is flat, with a root-mean-square roughness of 0.17 nm, which is much lower than that of conventional barrier materials. This flatness allows the utilization of a very thin but well-defined tunneling barrier, leading to a large spin signal of ˜20 Ω and a high spin injection efficiency of 15% with a low contact resistance of ˜1 kΩ. These findings represent important progress toward the realization of graphene-based spintronics applications.

  13. 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.

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

    PubMed Central

    2013-01-01

    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. PMID:23618313

  15. 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.

  16. Stress influence on high temperature oxide scale growth: Modeling and investigation on a thermal barrier coating system

    NASA Astrophysics Data System (ADS)

    Saillard, A.; Cherkaoui, M.; Capolungo, L.; Busso, E. P.

    2010-07-01

    In thermal barrier coating (TBC) systems, an oxide layer develops at high temperature below the ceramic coating, leading in the long term to the mechanical failure of the structure upon cooling. The mechanism of stress-affected oxidation likely to induce the growth of a non-uniform oxide scale detrimental to the TBC lifetime was investigated. A continuum thermodynamics formulation is derived accounting for the influence of the stress and strain situation at the sharp metal/oxide phase boundary on the local oxidation kinetics. It specially includes the contributions of the large volumetric strain and the mass consumption associated with metal oxidation. A continuum mechanics/mass diffusion framework is used along with the developed formulation for the interface evolution to study the growth of an oxide layer coupled with local stress development. The implementation of the model has required the development of a specific simulation tool, based on a finite element method completed with an external routine for the phase boundary propagation. Results on an electron-beam physical vapor deposited (EB-PVD) TBC case are presented. The processes resulting in a non-uniform oxide scale growth are analyzed and the main influences are discussed.

  17. Nitric oxide isoenzymes regulate lipopolysaccharide-enhanced insulin transport across the blood-brain barrier.

    PubMed

    Banks, William A; Dohgu, Shinya; Lynch, Jessica L; Fleegal-DeMotta, Melissa A; Erickson, Michelle A; Nakaoke, Ryota; Vo, Than Q

    2008-04-01

    Insulin transported across the blood-brain barrier (BBB) has many effects within the central nervous system. Insulin transport is not static but altered by obesity and inflammation. Lipopolysaccharide (LPS), derived from the cell walls of Gram-negative bacteria, enhances insulin transport across the BBB but also releases nitric oxide (NO), which opposes LPS-enhanced insulin transport. Here we determined the role of NO synthase (NOS) in mediating the effects of LPS on insulin BBB transport. The activity of all three NOS isoenzymes was stimulated in vivo by LPS. Endothelial NOS and inducible NOS together mediated the LPS-enhanced transport of insulin, whereas neuronal NOS (nNOS) opposed LPS-enhanced insulin transport. This dual pattern of NOS action was found in most brain regions with the exception of the striatum, which did not respond to LPS, and the parietal cortex, hippocampus, and pons medulla, which did not respond to nNOS inhibition. In vitro studies of a brain endothelial cell (BEC) monolayer BBB model showed that LPS did not directly affect insulin transport, whereas NO inhibited insulin transport. This suggests that the stimulatory effect of LPS and NOS on insulin transport is mediated through cells of the neurovascular unit other than BECs. Protein and mRNA levels of the isoenzymes indicated that the effects of LPS are mainly posttranslational. In conclusion, LPS affects insulin transport across the BBB by modulating NOS isoenzyme activity. NO released by endothelial NOS and inducible NOS acts indirectly to stimulate insulin transport, whereas NO released by nNOS acts directly on BECs to inhibit insulin transport. PMID:18187549

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

    SciTech Connect

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

    2015-10-22

    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. In this study, 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. In conclusion, 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.

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

    DOE PAGESBeta

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

    2015-10-22

    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. In this study, 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 usedmore » 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. In conclusion, 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.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    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.

  1. 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. PMID:26489518

  2. Scale-dependent bias from an inflationary bispectrum: the effect of a stochastic moving barrier

    NASA Astrophysics Data System (ADS)

    Biagetti, Matteo; Desjacques, Vincent

    2015-08-01

    With the advent of large-scale galaxy surveys, constraints on primordial non-Gaussianity (PNG) are expected to reach O(f_NL) ˜ 1. In order to fully exploit the potential of these future surveys, a deep theoretical understanding of the signatures imprinted by PNG on the large-scale structure of the Universe is necessary. In this paper, we explore the effect of a stochastic moving barrier on the amplitude of the non-Gaussian bias induced by local quadratic PNG. We show that, in the peak approach to halo clustering, the amplitude of the non-Gaussian bias will generally differ from the peak-background split prediction unless the barrier is flat and deterministic. For excursion set peaks with a square-root barrier, which reproduce reasonably well the linear bias b1 and mass function bar{n}_h of SO haloes, the non-Gaussian bias amplitude is ˜40 per cent larger than the peak-background split expectation partial lnbar{n}_h/partial lnσ _8 for haloes of mass ˜1013 M⊙ h-1 at z = 0. Furthermore, we argue that the effect of PNG on squeezed configurations of the halo bispectrum differs significantly from that predicted by standard local bias approaches. Our predictions can be easily confirmed, or invalidated, with N-body simulations.

  3. The toxicity of graphene oxides: dependence on the oxidative methods used.

    PubMed

    Chng, Elaine Lay Khim; Pumera, Martin

    2013-06-17

    Graphene, a class of two-dimensional carbon nanomaterial, has attracted extensive interest in recent years, with a significant amount of research focusing on graphene oxides (GOs). They have been primed as potential candidates for biomedical applications such as cell labeling and drug delivery, thus the toxicity and behavior of graphene oxides in biological systems are fundamental issues that need urgent attention. The production of GO is generally achieved through a top-down route, which includes the usage of concentrated H₂SO₄ along with: 1) concentrated nitric acid and KClO₃ oxidant (Hoffmann); 2) fuming nitric acid and KClO₃ oxidant (Staudenmaier); 3) concentrated phosphoric acid with KMnO₄ (Tour); or 4) sodium nitrate for in-situ production of nitric acid in the presence of KMnO₄ (Hummers). It has been widely assumed that the properties of these four GOs produced by using the above different methods are roughly similar, so the methods have been used interchangeably. However, several studies have reported that the toxicity of graphene-related nanomaterials in biological systems may be influenced by their physiochemical properties, such as surface functional groups and structural defects. In addition, considering how GOs are increasingly used in the field of biomedicine, we are interested to see how the oxygen content/functional groups of GOs can impact their toxicological profiles. Since in-vitro testing is a common first step in assessing the health risks related with engineered nanomaterials, the cytotoxicity of the GOs prepared by the four different oxidative treatments was investigated by measuring the mitochondrial activity in adherent lung epithelial cells (A549) by using commercially available viability assays. The dose-response data was generated by using two assays, the methylthiazolyldiphenyl-tetrazolium bromide (MTT) assay and the water-soluble tetrazolium salt (WST-8). From the viability data, it is evident that there is a strong dose-dependent

  4. 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.

  5. Oral administration of Bifidobacterium breve attenuates UV-induced barrier perturbation and oxidative stress in hairless mice skin.

    PubMed

    Ishii, Yuki; Sugimoto, Saho; Izawa, Naoki; Sone, Toshiro; Chiba, Katsuyoshi; Miyazaki, Kouji

    2014-07-01

    Recent studies have shown that some probiotics affect not only the gut but also the skin. However, the effects of probiotics on ultraviolet (UV)-induced skin damage are poorly understood. In this study, we aim to examine whether oral administration of live Bifidobacterium breve strain Yakult (BBY), a typical probiotic, can attenuate skin barrier perturbation caused by UV and reactive oxygen species (ROS) in hairless mice. The mice were orally supplemented with a vehicle only or BBY once a day for nine successive days. Mouse dorsal skin was irradiated with UV from days 6 to 9. The day after the final irradiation, the transepidermal water loss (TEWL), stratum corneum hydration, and oxidation-related factors of the skin were evaluated. We elucidated that BBY prevented the UV-induced increase in TEWL and decrease in stratum corneum hydration. In addition, BBY significantly suppressed the UV-induced increase in hydrogen peroxide levels, oxidation of proteins and lipids, and xanthine oxidase activity in the skin. Conversely, antioxidant capacity did not change regardless of whether BBY was administered or not. In parameters we evaluated, there was a positive correlation between the increase in TEWL and the oxidation levels of proteins and lipids. Our results suggest that oral administration of BBY attenuates UV-induced barrier perturbation and oxidative stress of the skin, and this antioxidative effect is not attributed to enhancement of antioxidant capacity but to the prevention of ROS generation. PMID:24414333

  6. 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.

  7. 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.

  8. Effect of Coating Process Condition on High-Temperature Oxidation and Mechanical Failure Behavior for Plasma Sprayed Thermal Barrier Coating Systems

    NASA Astrophysics Data System (ADS)

    Takahashi, Satoru; Yoshiba, Masayuki; Harada, Yoshio

    In order to clarify the thermal and/or mechanical failure behavior of the plasma sprayed thermal barrier coating (TBC) system in connection with their coating characteristics depending on the coating process condition, two kinds of the failure analytical tests were conducted for TBC systems processed under different conditions. One was the high-temperature oxidation test, which was conducted at 1100°C under both the isothermal and thermal cycle conditions. The other was the in-situ observation of mechanical failure behavior, which was conducted under the static loadings at ambient temperature; as the most fundamental aspect, by means of an optical microscopy. It was found that the thermal and mechanical failure behavior of TBC system depends strongly on the top-coat (TC)/bond-coat (BC) interfacial condition, the reheat-treatment (RHT) after spraying and so on. For the TBC system with vacuum plasma sprayed (VPS) BC as well as for that with atmospheric plasma sprayed (APS) BC, in particular, the RHT at an appropriate temperature in Ar atmosphere was found to be effective for improving the oxidation property. For the TBC system with APS-BC, however, it was impossible to prevent the crack growth into the BC interior under the tensile loading in spite of conducting the RHT, since the microdefects such as oxides within the APS-BC tend to provide an easy crack propagation path. Furthermore, it was clarified that the smoothening process on the BC surface is able to prevent perfectly the occurrence of the wart-like oxide during oxidation, but at the same time increases also the risk of the TC spalling under the mechanical loading.

  9. 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.

  10. Temperature dependence of photoemission from quantum-well states in Ag/V(100): Moving surface-vacuum barrier effects

    SciTech Connect

    Kralj, M.; Siber, A.; Pervan, P.; Milun, M.; Valla, T.; Johnson, P. D.; Woodruff, D. P.

    2001-08-15

    The temperature dependence of angle-resolved photoemission from quantum-well states in ultrathin films of Ag on V(100) has been examined for films from 1--8 ML thickness within the temperature range 45--600 K. Contrary to bulk solids, the photoemission peaks shift to higher binding energy as the temperature is increased. The temperature dependence of the peak widths is linear, consistent with the expected behavior for electron-phonon coupling, but the coupling parameter {lambda} is found to show a strong oscillatory dependence on film thickness, with some values many times larger than those found for bulk silver. The observations are explained in terms of the influence on both the initial and final states in the photoemission process of the static and dynamic movements of the surface-vacuum interface barrier induced by temperature changes.

  11. Site-dependent catalytic activity of graphene oxides towards oxidative dehydrogenation of propane.

    PubMed

    Tang, Shaobin; Cao, Zexing

    2012-12-28

    Graphene oxides (GOs) may offer extraordinary potential in the design of novel catalytic systems due to the presence of various oxygen functional groups and their unique electronic and structural properties. Using first-principles calculations, we explore the plausible mechanisms for the oxidative dehydrogenation (ODH) of propane to propene by GOs and the diffusion of the surface oxygen-containing groups under an external electric field. The present results show that GOs with modified oxygen-containing groups may afford high catalytic activity for the ODH of propane to propene. The presence of hydroxyl groups around the active sites provided by epoxides can remarkably enhance the C-H bond activation of propane and the activity enhancement exhibits strong site dependence. The sites of oxygen functional groups on the GO surface can be easily tuned by the diffusion of these groups under an external electric field, which increases the reactivity of GOs towards ODH of propane. The chemically modified GOs are thus quite promising in the design of metal-free catalysis. PMID:22801590

  12. DNA damage signalling barrier, oxidative stress and treatment-relevant DNA repair factor alterations during progression of human prostate cancer.

    PubMed

    Kurfurstova, Daniela; Bartkova, Jirina; Vrtel, Radek; Mickova, Alena; Burdova, Alena; Majera, Dusana; Mistrik, Martin; Kral, Milan; Santer, Frederic R; Bouchal, Jan; Bartek, Jiri

    2016-06-01

    The DNA damage checkpoints provide an anti-cancer barrier in diverse tumour types, however this concept has remained unexplored in prostate cancer (CaP). Furthermore, targeting DNA repair defects by PARP1 inhibitors (PARPi) as a cancer treatment strategy is emerging yet requires suitable predictive biomarkers. To address these issues, we performed immunohistochemical analysis of multiple markers of DNA damage signalling, oxidative stress, DNA repair and cell cycle control pathways during progression of human prostate disease from benign hyperplasia, through intraepithelial neoplasia to CaP, complemented by genetic analyses of TMPRSS2-ERG rearrangement and NQO1, an anti-oxidant factor and p53 protector. The DNA damage checkpoint barrier (γH2AX, pATM, p53) mechanism was activated during CaP tumorigenesis, albeit less and with delayed culmination compared to other cancers, possibly reflecting lower replication stress (slow proliferation despite cases of Rb loss and cyclin D1 overexpression) and progressive loss of ATM activator NKX3.1. Oxidative stress (8-oxoguanine lesions) and NQO1 increased during disease progression. NQO1 genotypes of 390 men did not indicate predisposition to CaP, yet loss of NQO1 in CaP suggested potential progression-opposing tumour suppressor role. TMPRSS2-ERG rearrangement and PTEN loss, events sensitizing to PARPi, occurred frequently along with heterogeneous loss of DNA repair factors 53BP1, JMJD1C and Rev7 (all studied here for the first time in CaP) whose defects may cause resistance to PARPi. Overall, our results reveal an unorthodox DNA damage checkpoint barrier scenario in CaP tumorigenesis, and provide novel insights into oxidative stress and DNA repair, with implications for biomarker guidance of future targeted therapy of CaP. PMID:26987799

  13. Insulin increases glomerular filtration barrier permeability through PKGIα-dependent mobilization of BKCa channels in cultured rat podocytes.

    PubMed

    Piwkowska, Agnieszka; Rogacka, Dorota; Audzeyenka, Irena; Kasztan, Małgorzata; Angielski, Stefan; Jankowski, Maciej

    2015-08-01

    Podocytes are highly specialized cells that wrap around glomerular capillaries and comprise a key component of the glomerular filtration barrier. They are uniquely sensitive to insulin; like skeletal muscle and fat cells, they exhibit insulin-stimulated glucose uptake and express glucose transporters. Podocyte insulin signaling is mediated by protein kinase G type I (PKGI), and it leads to changes in glomerular permeability to albumin. Here, we investigated whether large-conductance Ca²⁺-activated K⁺ channels (BKCa) were involved in insulin-mediated, PKGIα-dependent filtration barrier permeability. Insulin-induced glomerular permeability was measured in glomeruli isolated from Wistar rats. Transepithelial albumin flux was measured in cultured rat podocyte monolayers. Expression of BKCa subunits was detected by RT-PCR. BKCa, PKGIα, and upstream protein expression were examined in podocytes with Western blotting and immunofluorescence. The BKCa-PKGIα interaction was assessed with co-immunoprecipitation. RT-PCR showed that primary cultured rat podocytes expressed mRNAs that encoded the pore-forming α subunit and four accessory β subunits of BKCa. The BKCa inhibitor, iberiotoxin (ibTX), abolished insulin-dependent glomerular albumin permeability and PKGI-dependent transepithelial albumin flux. Insulin-evoked albumin permeability across podocyte monolayers was also blocked with BKCa siRNA. Moreover, ibTX blocked insulin-induced disruption of the actin cytoskeleton and changes in the phosphorylation of PKG target proteins, MYPT1 and RhoA. These results indicated that insulin increased filtration barrier permeability through mobilization of BKCa channels via PKGI in cultured rat podocytes. This molecular mechanism may explain podocyte injury and proteinuria in diabetes. PMID:25952906

  14. 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.

  15. Probiotic-derived polyphosphate improves the intestinal barrier function through the caveolin-dependent endocytic pathway.

    PubMed

    Tanaka, Kazuyuki; Fujiya, Mikihiro; Konishi, Hiroaki; Ueno, Nobuhiro; Kashima, Shin; Sasajima, Junpei; Moriichi, Kentaro; Ikuta, Katsuya; Tanabe, Hiroki; Kohgo, Yutaka

    2015-11-20

    Probiotics exhibit beneficial functions for host homeostasis maintenance. We herein investigated the mechanism by which Lactobacillus brevis-derived poly P exhibited a beneficial function. Immunostaining indicated that poly P was captured in the plasma membrane via integrin β1 in Caco2/bbe cells. The uptake of poly P was reduced by the inhibition of integrin β1 as well as caveolin-1, a major component of lipid rafts. The function of poly P, including the induction of HSP27 and enhancement of the intestinal barrier function, was suppressed by the inhibition of caveolin-1, illustrating that the function of poly P was mediated by the endocytic pathway. High-throughput sequencing revealed that poly P induced tumor necrosis factor alpha-induced protein 3, which contributes to cytoprotection, including upregulation of the intestinal barrier function. The present study demonstrates a novel host-probiotic interaction through the uptake of bacterial substance into host cells, which is distinct from pattern recognition receptor pathways. PMID:26459590

  16. 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

  17. 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.

  18. Solution phase synthesis and intense pulsed light sintering and reduction of a copper oxide ink with an encapsulating nickel oxide barrier

    NASA Astrophysics Data System (ADS)

    Jha, M.; Dharmadasa, R.; Draper, G. L.; Sherehiy, A.; Sumanasekera, G.; Amos, D.; Druffel, T.

    2015-05-01

    Copper oxide nanoparticle inks sintered and reduced by intense pulsed light (IPL) are an inexpensive means to produce conductive patterns on a number of substrates. However, the oxidation and diffusion characteristics of copper are issues that must be resolved before it can be considered as a viable solution. Nickel can provide a degree of oxidation protection and act as a barrier for the diffusion of copper. In the present study we have for the first time synthesized copper oxide with an encapsulating nickel oxide nanostructure using a solution phase synthesis process in the presence of a surfactant at room temperature. The room temperature process enables us to easily prevent the formation of alloys at the copper-nickel interface. The synthesis results in a simple technique (easily commercializable, tested at a 10 g scale) with highly controllable layer thicknesses on a 20 nm copper oxide nanoparticle. These Cu2O@NiO dispersions were then directly deposited onto substrates and sintered/reduced using an IPL source. The sintering technique produces a highly conductive film with very short processing times. Films have been deposited onto silicon, and the copper-nickel structure has shown a lower copper diffusion. The nanostructures and resulting films were characterized using electron and x-ray spectroscopy, and the films’ resistivity was measured.

  19. Barriers to intramolecular rotation determined from the temperature dependence of the Henry constant in the region of adsorbed molecule rigidity failure

    NASA Astrophysics Data System (ADS)

    Dolgonosov, A. M.; Prudkovskii, A. G.

    2008-05-01

    A distribution for the rigid and nonrigid adsorbed molecule forms was found. Adsorbed molecule rigidity failure was shown to be accompanied by a weak nonlinear effect, which manifested itself as a temperature dependence of the Henry constant. A method for the determination of the barrier to intramolecular rotation from the temperature dependence of the molecule adsorption constant was suggested. Barriers to rotation about the C-C and C-O bonds were determined for several molecules.

  20. 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.

  1. Size dependence of inter- and intra-cluster interactions in core-shell iron-iron oxide nanoclusters

    SciTech Connect

    Kaur, Maninder; McCloy, John S.; Jiang, Weilin; Yao, Qi; Qiang, You

    2012-06-15

    The room temperature magnetic properties of core-shell iron-iron oxide nanoclusters (NCs) synthesized by a cluster deposition system have been investigated, and their dependence on mean cluster size has been discussed. In this study, the surface/boundary spins of clusters were not frozen and were thermally activated during the measurements. The inter-cluster interactions between clusters and intra-cluster interactions between the iron core (ferromagnetic) and iron oxide shell (ferrimagnetic) have been investigated by field dependent isothermal remanent magnetization and dc demagnetization measurements at room temperature. The Henkel plot and delta M plot support the existence of dipolar inter-cluster interactions which become stronger with the growth of cluster size. The derivative of the initial magnetization curve implies that smaller clusters require less field and time than the bigger ones to overcome various energy barriers before aligning along the field direction. Coercive field and magnetization are also correlated with the interaction parameters. To compare the room temperature magnetic results, one system was studied at low temperature, where exchange coupling at the interface between the oxide and metallic phases was observed through bias effect and anisotropy enhancement.

  2. 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

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

    PubMed

    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

  4. Quantum state-resolved CH4 dissociation on Pt(111): coverage dependent barrier heights from experiment and density functional theory.

    PubMed

    Ueta, Hirokazu; Chen, Li; Beck, Rainer D; Colón-Dìaz, Inara; Jackson, Bret

    2013-12-21

    The dissociative chemisorption of CH4 on Pt(111) was studied using quantum state-resolved methods at a surface temperature (T(s)) of 150 K where the nascent reaction products CH3(ads) and H(ads) are stable and accumulate on the surface. Most previous experimental studies of methane chemisorption on transition metal surfaces report only the initial sticking coefficients S0 on a clean surface. Reflection absorption infrared spectroscopy (RAIRS), used here for state resolved reactivity measurements, enables us to monitor the CH3(ads) uptake during molecular beam deposition as a function of incident translational energy (E(t)) and vibrational state (ν3 anti-symmetric C-H stretch of CH4) to obtain the initial sticking probability S0, the coverage dependence of the sticking probability S(θ) and the CH3(ads) saturation coverage θ(sat). We observe that both S0 and θ(sat) increase with increasing E(t) as well as upon ν3 excitation of the incident CH4 which indicates a coverage dependent dissociation barrier height for the dissociation of CH4 on Pt(111) at low surface temperature. This interpretation is supported by density functional calculations of barrier heights for dissociation, using large supercells containing one or more H and/or methyl adsorbates. We find a significant increase in the activation energies with coverage. These energies are used to construct simple models that reasonably reproduce the uptake data and the observed saturation coverages. PMID:24177276

  5. Partial oxidation of methane to methanol with nitrogen dioxide in dielectric barrier discharge plasma: experimental and molecular modeling

    NASA Astrophysics Data System (ADS)

    Indarto, Antonius

    2016-04-01

    Non-catalytic conversion of methane (CH4) and nitrogen dioxide (NO2) into methanol (CH3OH) has been conducted and presented in this paper. Experiments were carried out using dielectric barrier discharge as the reaction medium in atmospheric pressure and temperature conditions. High yield production of methanol was achieved (18-20% mol) by single-stage plasma reaction with maximum selectivity of 32% mol. Compared to other oxidants, such as O2, the presence of NO2 in the plasma reaction resulted in higher methanol selectivity. For better understanding of the reactions, density functional theory calculations were also performed and discussed.

  6. 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...

  7. Compositionally Graded Thermal Barrier Coating by Hybrid Thermal Spraying Route and its Non-isothermal Oxidation Behavior

    NASA Astrophysics Data System (ADS)

    Nath, Subhasisa; Manna, Indranil; Dutta Majumdar, Jyotsna

    2013-08-01

    The present study concerns a detailed investigation of the characteristics and oxidation resistance property of a duplex and compositionally graded thermal barrier coating on Inconel 718. The duplex coating consists of a CoNiCrAlY bond coat layer sprayed on to sand-blasted Inconel 718 substrate (by high velocity oxy-fuel spraying) followed by deposition of a yttria-stabilized zirconia (YSZ) top coat by plasma spraying. The compositionally graded coating consists of several layers deposited by plasma spraying of pre-mixed CoNiCrAlY and YSZ powders in the weight ratios of 70:30, 50:50, 30:70, and 0:100 varying from the bond coat to the top surface, respectively. A detailed investigation of the microstructure, composition, and phases in the coating and its non-isothermal oxidation behavior from room temperature to 1250°C was performed. Oxidation proceeds by three stages in the as-received Inconel 718 and the compositionally graded coating, but by two stages in the duplex coating with a maximum activation energy for oxidation in the compositionally graded coating at high temperature (stage III). The kinetics and mechanism of oxidation were established.

  8. 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.

  9. Oxidative Stress-Dependent Coronary Endothelial Dysfunction in Obese Mice

    PubMed Central

    Gamez-Mendez, Ana María; Vargas-Robles, Hilda; Ríos, Amelia; Escalante, Bruno

    2015-01-01

    Obesity is involved in several cardiovascular diseases including coronary artery disease and endothelial dysfunction. Endothelial Endothelium vasodilator and vasoconstrictor agonists play a key role in regulation of vascular tone. In this study, we evaluated coronary vascular response in an 8 weeks diet-induced obese C57BL/6 mice model. Coronary perfusion pressure in response to acetylcholine in isolated hearts from obese mice showed increased vasoconstriction and reduced vasodilation responses compared with control mice. Vascular nitric oxide assessed in situ with DAF-2 DA showed diminished levels in coronary arteries from obese mice in both basal and acetylcholine-stimulated conditions. Also, released prostacyclin was decreased in heart perfusates from obese mice, along with plasma tetrahydrobiopterin level and endothelium nitric oxide synthase dimer/monomer ratio. Obesity increased thromboxane A2 synthesis and oxidative stress evaluated by superoxide and peroxynitrite levels, compared with control mice. Obese mice treated with apocynin, a NADPH oxidase inhibitor, reversed all parameters to normal levels. These results suggest that after 8 weeks on a high-fat diet, the increase in oxidative stress lead to imbalance in vasoactive substances and consequently to endothelial dysfunction in coronary arteries. PMID:26381906

  10. Schottky barrier height of Au on the transparent semiconducting oxide β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Mohamed, M.; Irmscher, K.; Janowitz, C.; Galazka, Z.; Manzke, R.; Fornari, R.

    2012-09-01

    The Schottky barrier height of Au deposited on (100) surfaces of n-type β-Ga2O3 single crystals was determined by current-voltage characteristics and high-resolution photoemission spectroscopy resulting in a common effective value of 1.04 ± 0.08 eV. Furthermore, the electron affinity of β-Ga2O3 and the work function of Au were determined to be 4.00 ± 0.05 eV and 5.23 ± 0.05 eV, respectively, yielding a barrier height of 1.23 eV according to the Schottky-Mott rule. The reduction of the Schottky-Mott barrier to the effective value was ascribed to the image-force effect and the action of metal-induced gap states, whereas extrinsic influences could be avoided.

  11. Selenium and vitamin E together improve intestinal epithelial barrier function and alleviate oxidative stress in heat-stressed pigs.

    PubMed

    Liu, Fan; Cottrell, Jeremy J; Furness, John B; Rivera, Leni R; Kelly, Fletcher W; Wijesiriwardana, Udani; Pustovit, Ruslan V; Fothergill, Linda J; Bravo, David M; Celi, Pietro; Leury, Brian J; Gabler, Nicholas K; Dunshea, Frank R

    2016-07-01

    What is the central question of this study? Oxidative stress may play a role in compromising intestinal epithelial barrier integrity in pigs subjected to heat stress, but it is unknown whether an increase of dietary antioxidants (selenium and vitamin E) could alleviate gut leakiness in heat-stressed pigs. What is the main finding and its importance? Levels of dietary selenium (1.0 p.p.m.) and vitamin E (200 IU kg(-1) ) greater than those usually recommended for pigs reduced intestinal leakiness caused by heat stress. This finding suggests that oxidative stress plays a role in compromising intestinal epithelial barrier integrity in heat-stressed pigs and also provides a nutritional strategy for mitigating these effects. Heat stress compromises the intestinal epithelial barrier integrity of mammals through mechanisms that may include oxidative stress. Our objective was to test whether dietary supplementation with antioxidants, selenium (Se) and vitamin E (VE), protects intestinal epithelial barrier integrity in heat-stressed pigs. Female growing pigs (n = 48) were randomly assigned to four diets containing from 0.2 p.p.m. Se and 17 IU kg(-1) VE (control, National Research Council recommended) to 1.0 p.p.m. Se and 200 IU kg(-1) VE for 14 days. Six pigs from each dietary treatment were then exposed to either thermoneutral (20°C) or heat-stress conditions (35°C 09.00-17.00 h and 28°C overnight) for 2 days. Transepithelial electrical resistance and fluorescein isothiocyanate-dextran (4 kDa; FD4) permeability were measured in isolated jejunum and ileum using Ussing chambers. Rectal temperature, respiratory rate and intestinal HSP70 mRNA abundance increased (all P < 0.001), and respiratory alkalosis occurred, suggesting that pigs were heat stressed. Heat stress also increased FD4 permeability and decreased transepithelial electrical resistance (both P < 0.01). These changes were associated with changes indicative of oxidative stress, a decreased

  12. Haptoglobin Genotype-dependent Differences in Macrophage Lysosomal Oxidative Injury*

    PubMed Central

    Asleh, Rabea; Ward, John; Levy, Nina S.; Safuri, Shady; Aronson, Doron; Levy, Andrew P.

    2014-01-01

    The major function of the Haptoglobin (Hp) protein is to control trafficking of extracorpuscular hemoglobin (Hb) thru the macrophage CD163 receptor with degradation of the Hb in the lysosome. There is a common copy number polymorphism in the Hp gene (Hp 2 allele) that has been associated with a severalfold increased incidence of atherothrombosis in multiple longitudinal studies. Increased plaque oxidation and apoptotic markers have been observed in Hp 2-2 atherosclerotic plaques, but the mechanism responsible for this finding has not been determined. We proposed that the increased oxidative injury in Hp 2-2 plaques is due to an impaired processing of Hp 2-2-Hb complexes within macrophage lysosomes, thereby resulting in redox active iron accumulation, lysosomal membrane oxidative injury, and macrophage apoptosis. We sought to test this hypothesis in vitro using purified Hp-Hb complex and cells genetically manipulated to express CD163. CD163-mediated endocytosis and lysosomal degradation of Hp-Hb were decreased for Hp 2-2-Hb complexes. Confocal microscopy using lysotropic pH indicator dyes demonstrated that uptake of Hp 2-2-Hb complexes disrupted the lysosomal pH gradient. Cellular fractionation studies of lysosomes isolated from macrophages incubated with Hp 2-2-Hb complexes demonstrated increased lysosomal membrane oxidation and a loss of lysosomal membrane integrity leading to lysosomal enzyme leakage into the cytoplasm. Additionally, markers of apoptosis, DNA fragmentation, and active caspase 3 were increased in macrophages that had endocytosed Hp 2-2-Hb complexes. These data provide novel mechanistic insights into how the Hp genotype regulates lysosomal oxidative stress within macrophages after receptor-mediated endocytosis of Hb. PMID:24778180

  13. 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.

  14. Tumor Necrosis Factor Disrupts Claudin-5 Endothelial Tight Junction Barriers in Two Distinct NF-κB-Dependent Phases

    PubMed Central

    Clark, Paul R.; Kim, Richard K.; Pober, Jordan S.; Kluger, Martin S.

    2015-01-01

    Capillary leak in severe sepsis involves disruption of endothelial cell tight junctions. We modeled this process by TNF treatment of cultured human dermal microvascular endothelial cell (HDMEC) monolayers, which unlike human umbilical vein endothelial cells form claudin-5-dependent tight junctions and a high-resistance permeability barrier. Continuous monitoring with electrical cell-substrate impedance sensing revealed that TNF disrupts tight junction-dependent HDMEC barriers in discrete steps: an ~5% increase in transendothelial electrical resistance over 40 minutes; a decrease to ~10% below basal levels over 2 hours (phase 1 leak); an interphase plateau of 1 hour; and a major fall in transendothelial electrical resistance to < 70% of basal levels by 8–10 hours (phase 2 leak), with EC50 values of TNF for phase 1 and 2 leak of ~30 and ~150 pg/ml, respectively. TNF leak is reversible and independent of cell death. Leak correlates with disruption of continuous claudin-5 immunofluorescence staining, myosin light chain phosphorylation and loss of claudin-5 co-localization with cortical actin. All these responses require NF-κB signaling, shown by inhibition with Bay 11 or overexpression of IκB super-repressor, and are blocked by H-1152 or Y-27632, selective inhibitors of Rho-associated kinase that do not block other NF-κB-dependent responses. siRNA combined knockdown of Rho-associated kinase-1 and -2 also prevents myosin light chain phosphorylation, loss of claudin-5/actin co-localization, claudin-5 reorganization and reduces phase 1 leak. However, unlike H-1152 and Y-27632, combined Rho-associated kinase-1/2 siRNA knockdown does not reduce the magnitude of phase 2 leak, suggesting that H-1152 and Y-27632 have targets beyond Rho-associated kinases that regulate endothelial barrier function. We conclude that TNF disrupts TJs in HDMECs in two distinct NF-κB-dependent steps, the first involving Rho-associated kinase and the second likely to involve an as yet

  15. In Situ Chemical Oxidation of Contaminated Ground Water: Permanganate Reactive Barrier Systems for the Long-Term Treatment of Contaminants

    SciTech Connect

    Li, X. David; Schwartz, Frank W.

    2004-03-31

    Oxidation of chlorinated solvents by permanganate has proven to be effective in destroying these compounds in the aqueous phase. A semi-passive, well-based permanganate reactive barrier system (PRBS) was designed in order for the long-term treatment of dissolved contaminant in the ground water. Results from laboratory experiments indicate the PRBS could deliver permanganate at a stable, constant and controllable rate. In this paper, different field designs of the PRBS are discussed. Numerical simulation was conducted to elucidate the parameters that will influence the field implementation of a PRBS. We investigated issues such as permanganate consumption by aquifer materials, variable density flow effect, as well as lateral spreading under different geological settings. Results from this study continue to point to the promise of an in situ chemical oxidation scheme. PRBS provides a potential treatment of the contaminated ground water at relatively low management cost as compared with other alternatives.

  16. Purinergic receptor P2RY12-dependent microglial closure of the injured blood-brain barrier.

    PubMed

    Lou, Nanhong; Takano, Takahiro; Pei, Yong; Xavier, Anna L; Goldman, Steven A; Nedergaard, Maiken

    2016-01-26

    Microglia are integral functional elements of the central nervous system, but the contribution of these cells to the structural integrity of the neurovascular unit has not hitherto been assessed. We show here that following blood-brain barrier (BBB) breakdown, P2RY12 (purinergic receptor P2Y, G-protein coupled, 12)-mediated chemotaxis of microglia processes is required for the rapid closure of the BBB. Mice treated with the P2RY12 inhibitor clopidogrel, as well as those in which P2RY12 was genetically ablated, exhibited significantly diminished movement of juxtavascular microglial processes and failed to close laser-induced openings of the BBB. Thus, microglial cells play a previously unrecognized protective role in the maintenance of BBB integrity following cerebrovascular damage. Because clopidogrel antagonizes the platelet P2Y12 receptor, it is widely prescribed for patients with coronary artery and cerebrovascular disease. As such, these observations suggest the need for caution in the postincident continuation of P2RY12-targeted platelet inhibition. PMID:26755608

  17. Temperature-Dependent Current-Voltage (I-V) and Capacitance-Voltage (C-V) Characteristics of Ni/Cu/n-InP Schottky Barrier Diodes

    NASA Astrophysics Data System (ADS)

    Munikrishana Reddy, Y.; Nagaraj, M. K.; Siva Pratap Reddy, M.; Lee, Jung-Hee; Rajagopal Reddy, V.

    2013-04-01

    The current-voltage (I-V) and capacitance-voltage (C-V) characteristics of Ni/Cu/n-InP Schottky barrier diodes are studied over a wide temperature range, from 210 K to 420 K. The I-V characteristics display anomalous thermal behavior. The apparent barrier height decays, and the ideality factor grows at low temperatures, and the series resistances resulting from Cheung's and Norde's procedures are markedly temperature dependent. The nonlinearity of the Richardson plot and the strong temperature dependence of the Schottky-barrier parameters indicate that the interface is spatially inhomogeneous. Plots of the zero-bias barrier height as a function of 1/(2kT) points to a Gaussian distribution of barrier heights with 0.90 eV mean height and 0.014 eV standard deviation. When this distribution is accounted for, a Richardson of 6.5 A/(cm K)2 results, relatively close to the 9.4/(cm K)2 predicted by theory. We conclude that, combined with a Gaussian distribution of barrier heights, the thermionic-emission mechanism explains the temperature-dependent I-V and C-V characteristics of the studied Schottky-barrier diodes.

  18. 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.

  19. Racial Differences in Nitric Oxide-Dependent Vasorelaxation

    PubMed Central

    Mata-Greenwood, Eugenia; Chen, Dong-Bao

    2008-01-01

    Along with the growing heterogeneity of the American population, ethnic/racial disparity is becoming a clear health issue in the United States. The awareness of ethnic/racial disparities has been growing because of considerable data gathered from recent clinical and epidemiological studies. These studies have highlighted the importance of addressing these differences in the diagnosis and treatment of various diseases potentially according to race. It is becoming particularly clear that there is a 2- to 3-fold racial difference in certain cardiovascular diseases (eg, preeclampsia) associated with dysfunctional nitric oxide–mediated vasodilation. In this review, the authors summarize the current literature on racial disparities in nitric oxide–mediated vasodilation in relation to cardiovascular health with an emphasis on vascular nitric oxide bioavailability as a balance between production via endothelial nitric oxide synthase and degradation through reactive oxygen species. The major hypotheses postulated on the biological basis of these differences are also highlighted. PMID:18212350

  20. 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.

  1. 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. PMID:23999527

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    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.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

  3. 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.

  4. 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. PMID:25390073

  5. 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.

  6. Size-dependent thermal oxidation of copper: single-step synthesis of hierarchical nanostructures

    NASA Astrophysics Data System (ADS)

    Love, Christopher J.; Smith, J. David; Cui, Yuehua; Varanasi, Kripa K.

    2011-12-01

    Thermal oxidation of copper is a simple and scalable method to produce copper oxide nanowires. We report for the first time the formation of nanowires on copper powder during thermal oxidation and the resulting nanowire coverage that is dependent on the initial particle size. Systematic thermogravimetric analysis (TGA) and in situ X-ray diffraction (XRD) studies of thermal oxidation of particles of different sizes provide insights into the size-dependent process and evolution of the various phases of copper and copper oxide with time. Furthermore, we find that a large void is formed within these particles after oxidation and propose a mechanism based on the Kirkendall effect. The unique tunability of hierarchical features and hollow interior can be used to create new scalable structures for applications in a variety of areas including thermal management and catalysis.Thermal oxidation of copper is a simple and scalable method to produce copper oxide nanowires. We report for the first time the formation of nanowires on copper powder during thermal oxidation and the resulting nanowire coverage that is dependent on the initial particle size. Systematic thermogravimetric analysis (TGA) and in situ X-ray diffraction (XRD) studies of thermal oxidation of particles of different sizes provide insights into the size-dependent process and evolution of the various phases of copper and copper oxide with time. Furthermore, we find that a large void is formed within these particles after oxidation and propose a mechanism based on the Kirkendall effect. The unique tunability of hierarchical features and hollow interior can be used to create new scalable structures for applications in a variety of areas including thermal management and catalysis. Electronic supplementary information (ESI) available: SEM images, XRD spectra, and calculations. See DOI: 10.1039/c1nr10993f

  7. 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. PMID:27137132

  8. Removal of nitric oxide in flue gases by multipoint to plane dielectric barrier discharge

    SciTech Connect

    Takaki, Koichi; Jani, M.A.; Fujiwara, Tamiya

    1999-08-01

    An experimental study on the removal of NO{sub x} in flue gas has been carried out using plasma chemical reactions in a dielectric barrier discharge. A multipoint-to-plane geometry is used for electrode to lower the operating voltage. The effect of the multipoint electrode configuration on the characteristics of a discharge and NO{sub x} removal has been investigated. Plasma is produced in a narrow gap by a dielectric barrier discharge at low applied voltage with sinusoidal waveform of 2--3 kV rms Specific energy to reduce NO is 63 eV. Electric energy consumed in the discharge increases linearly with area of multipoint electrode, and is approximately 1 {micro}J/point at 2.7 kV. In regard to the multipoint electrode configuration, the consumed energy can be increased by making angle of the point small. However, the energy efficiency of NO removal becomes small if the point angle is small. It also decreases with reducing the number of points per unit area. In regard to treatment of exhaust gas from a diesel engine generator (20 kVA), NO can be almost completely depleted by the multipoint-to-plane barrier discharge for electrical load below 35% of the rated output.

  9. 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. PMID:27130561

  10. 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.

  11. Blood-Brain Barrier Disruption and Oxidative Stress in Guinea Pig after Systemic Exposure to Modified Cell-Free Hemoglobin

    PubMed Central

    Butt, Omer I.; Buehler, Paul W.; D'Agnillo, Felice

    2011-01-01

    Systemic exposure to cell-free hemoglobin (Hb) or its breakdown products after hemolysis or with the use of Hb-based oxygen therapeutics may alter the function and integrity of the blood-brain barrier. Using a guinea pig exchange transfusion model, we investigated the effect of a polymerized cell-free Hb (HbG) on the expression of endothelial tight junction proteins (zonula occludens 1, claudin-5, and occludin), astrocyte activation, IgG extravasation, heme oxygenase (HO), iron deposition, oxidative end products (4-hydroxynonenal adducts and 8-hydroxydeoxyguanosine), and apoptosis (cleaved caspase 3). Reduced zonula occludens 1 expression was observed after HbG transfusion as evidenced by Western blot and confocal microscopy. Claudin-5 distribution was altered in small- to medium-sized vessels. However, total expression of claudin-5 and occludin remained unchanged except for a notable increase in occludin 72 hours after HbG transfusion. HbG-transfused animals also showed increased astrocytic glial fibrillary acidic protein expression and IgG extravasation after 72 hours. Increased HO activity and HO-1 expression with prominent enhancement of HO-1 immunoreactivity in CD163-expressing perivascular cells and infiltrating monocytes/macrophages were also observed. Consistent with oxidative stress, HbG increased iron deposition, 4-hydroxynonenal and 8-hydroxydeoxyguanosine immunoreactivity, and cleaved caspase-3 expression. Systemic exposure to an extracellular Hb triggers blood-brain barrier disruption and oxidative stress, which may have important implications for the use of Hb-based therapeutics and may provide indirect insight on the central nervous system vasculopathies associated with excessive hemolysis. PMID:21356382

  12. 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

  13. Novel thermal barrier coatings (TBCs) that are resistant to high temperature attack by calcium oxide-magnesium oxide-silicon oxide-aluminum oxide (CMAS) glassy deposits

    NASA Astrophysics Data System (ADS)

    Aygun, Aysegul

    2008-10-01

    Higher performance and durability requirements of gas-turbine engines will require a new generation of thermal barrier coatings (TBCs). This is particularly true of engines operated at higher temperatures, where TBCs are subjected to attack by CaO-MgO-Al2O3-SiO 2 (CMAS) glassy deposits. In this work, a new approach for mitigating CMAS attack on TBCs is introduced, where up to 20 mol% Al2O 3 and 5 mol% TiO2 in the form of a solid solution is incorporated into Y2O3-stabilized ZrO2 (YSZ) TBCs. The fabrication of such TBCs with engineered chemistries is made possible by the solution-precursor plasma spray (SPPS) process, which is uniquely suited for depositing coatings of metastable ceramics with extended solid-solubilities. In the current work, the TBC serves as a reservoir of Al and Ti solutes, which are incorporated into the molten CMAS glass that is in contact with the TBC. An accumulation of Al concentration in the CMAS glass as it penetrates the TBC shifts the glass composition from the difficult-to-crystallize psuedowollastonite field to the easy-to-crystallize anorthite field. The incorporation of Ti in the glass promotes crystallization of the CMAS glass by serving as a nucleating agent. This combined effect results in the near-complete crystallization of the leading edge of the CMAS front into anorthite, essentially arresting the front. Both of these phenomena will help crystallize the CMAS glass, making it immobile and ineffective in penetrating the TBC. It is shown that incorporation of both Al and Ti in the CMAS glass is essential for this approach to be effective. Additionally, incorporation of Al and Ti as solutes is expected to alleviate thermal-expansion and thermal-conductivity issues associated with crystalline second phases used before. Moreover, the metastable nature of the Al and Ti solutes will make them more readily available for incorporation in the molten CMAS glass. CMAS interactions with SPPS TBCs of various metastable compositions are

  14. Nitrate-dependent anaerobic methane oxidation in a freshwater sediment

    NASA Astrophysics Data System (ADS)

    Norði, Katrin á.; Thamdrup, Bo

    2014-05-01

    Anaerobic oxidation of methane coupled to denitrification (DAOM) is a novel process of potential importance to the regulation of methane emissions from freshwater environments. We established nitrate-enriched microcosms of sediment from a freshwater pond in order to quantify the role of this process in a simulated natural redox zonation. The microcosms were allowed to acclimate to nitrate levels of 1-2 mmol L-1 in the overlying water for 16 months leading to a nitrate penetration of 4 cm. The nitrate enrichment significantly stimulated AOM relative to controls, and based on the similar concentrations of sulfate and reactive Fe(III) in the control sediment we conclude that the observed AOM was coupled to denitrification. DAOM occurred at rates that were two orders of magnitude lower than aerobic methane oxidation rates reported in freshwater sediments, and the process appeared to be limited by nitrate or nitrite even at millimolar nitrate concentrations. By contrast, ammonium was efficiently consumed at the base of the nitrate zone, presumably by the anammox process. Although DAOM was stimulated by nitrate enrichment, there were no significant differences between the methane emission from the control and nitrate-enriched microcosms. Our results provide the first experimental evaluation of the kinetics of DAOM in whole sediment cores and indicate that AOM coupled to denitrification can consume a substantial part of the methane flux in nitrate-rich environments. Because it is much less efficient in scavenging methane than its aerobic counterpart, the anaerobic process will, however, mainly be of significance in the regulation of methane emission from oxygen-depleted systems.

  15. Size-dependent electrical conductivity of indium zinc oxide deposited by RF magnetron sputtering.

    PubMed

    Heo, Young-Woo; Pearton, S J; Norton, D P

    2012-04-01

    We investigated the size-dependent electrical conductivities of indium zinc oxide stripes with different widths from 50 nm to 4 microm and with the same thickness of 50 nm deposited by RF magnetron sputtering. The size of the indium zinc oxide stripes was controlled by e-beam lithography. The distance of the two Ti/Au Ohmic electrodes along the indium zinc oxide stripes was kept constant at 25 microm. The electrical conductivity decreased as the size of the indium zinc oxide stripes decreased below a critical width (80 nm). The activation energy, derived from the electric conductivity versus temperature measurement, was dependent on the dimensions of indium zinc oxide stripes. These results can be understood as stemming from surface charge trapping from the absorption of oxygen and/or water vapor, which leads to an increase in the energy difference between the conduction energy band and the Fermi energy. PMID:22849102

  16. 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

  17. Field-induced macroscopic barrier model for persistent photoconductivity in nanocrystalline oxide thin-film transistors

    NASA Astrophysics Data System (ADS)

    Choi, Hyun-Sik; Jeon, Sanghun

    2014-03-01

    Persistent photoconductivity (PPC) in nanocrystalline InZnO thin-film transistors (TFTs) was studied using carrier fluctuation measurements and transient analysis. Low-frequency noise measurements and decay kinetics indicate that the band bending by the external field together with the ionized oxygen vacancy (Vo++) generated during the light exposure is the main cause of the PPC phenomenon. Based on these observations, a field-induced macroscopic barrier model is proposed as the origin of PPC for InZnO TFTs. In particular, this model explains that the carrier separation between e and Vo++ is induced by the external field applied to the three electrodes inside the transistor.

  18. 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

  19. 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

  20. Communication: Transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields

    NASA Astrophysics Data System (ADS)

    Craven, Galen T.; Bartsch, Thomas; Hernandez, Rigoberto

    2014-07-01

    When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product—for example, an energy barrier—becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories.

  1. 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...

  2. On determining the height of the potential barrier at grain boundaries in ion-conducting oxides.

    PubMed

    Kim, Sangtae; Kim, Seong K; Khodorov, Sergey; Maier, Joachim; Lubomirsky, Igor

    2016-01-28

    The validity and limitations of two quantitative approaches for estimating the height of the potential barrier at grain boundaries, Ψgb, in polycrystalline ionic conductors are examined both theoretically and experimentally. The linear diffusion model recently proposed by Kim and Lubomirsky determines Ψgb from the value of the power exponent of the current (Igb)-voltage (Ugb) relationship at the grain boundary, dln(Igb)/dln(Ugb), while the conventional approach calculates Ψgb from the ratio of the grain boundary resistivity to the grain core resistivity. The results of our theoretical analysis demonstrate that both approaches should yield consistent values for Ψgb if the ionic current through the grain boundary is limited exclusively by space charge. While the value of Ψgb obtained by the power law procedure is relatively insensitive to other causes of current obstruction, e.g. current constriction and/or local structural disorder, the resistivity ratio method, if not explicitly corrected for these additional limitations, results in a considerable overestimate of the grain boundary potential barrier. Hence, it is possible to distinguish between grain boundary resistance due to the presence of space charge and that due to additional sources by comparing the values of Ψgb determined using each of the two methods. Our theoretical analysis is confirmed experimentally with 3 mol% Gd-doped ceria with and without an additional source of current constriction across the grain boundary. PMID:26738808

  3. Electrophoretic deposition of diffusion barrier titanium oxide coatings for nuclear reactor cladding applications

    NASA Astrophysics Data System (ADS)

    Firouzdor, Vahid; Brechtl, Jamieson; Hauch, Benjamin; Sridharan, Kumar; Allen, Todd R.

    2013-10-01

    Development of TiO2 diffusion barrier coating by electrophoretic deposition (EPD) has been studied to mitigate fuel-cladding chemical interactions (FCCI). Important EPD deposition parameters, including solvent, additives, particle size and crystal structure, current, and voltage were optimized for coating deposition on flat T91 ferritic steel substrates. Post-deposition sintering in the range of 850-1050 °C was investigated. Diffusion characteristics of the coatings were evaluated by diffusion couple experiments at 575 °C for 100 h using cerium as one of the fission products responsible for FCCI. Results showed that the coated steel exhibited up to 83% reduction in solid state inter-diffusion with cerium. Heat transfer calculations showed that the fuel center-line temperature would increase slightly due to the addition of the TiO2 diffusion barrier coating; however, the maximum temperature still remains well below the melting point of uranium and is even lower than eutectic temperature between Fe2U and Fe2U6 at cladding centerline and cladding/fuel interface, respectively.

  4. The Endothelium-Dependent Nitric Oxide-cGMP Pathway.

    PubMed

    Mónica, F Z; Bian, K; Murad, F

    2016-01-01

    Nitric oxide (NO)-cyclic 3'-5' guanosine monophosphate (cGMP) signaling plays a critical role on smooth muscle tone, platelet activity, cardiac contractility, renal function and fluid balance, and cell growth. Studies of the 1990s established endothelium dysfunction as one of the major causes of cardiovascular diseases. Therapeutic strategies that benefit NO bioavailability have been applied in clinical medicine extensively. Basic and clinical studies of cGMP regulation through activation of soluble guanylyl cyclase (sGC) or inhibition of cyclic nucleotide phosphodiesterase type 5 (PDE5) have resulted in effective therapies for pulmonary hypertension, erectile dysfunction, and more recently benign prostatic hyperplasia. This section reviews (1) how endothelial dysfunction and NO deficiency lead to cardiovascular diseases, (2) how soluble cGMP regulation leads to beneficial effects on disorders of the circulation system, and (3) the epigenetic regulation of NO-sGC pathway components in the cardiovascular system. In conclusion, the discovery of the NO-cGMP pathway revolutionized the comprehension of pathophysiological mechanisms involved in cardiovascular and other diseases. However, considering the expression "from bench to bedside" the therapeutic alternatives targeting NO-cGMP did not immediately follow the marked biochemical and pathophysiological revolution. Some therapeutic options have been effective and released on the market for pulmonary hypertension and erectile dysfunction such as inhaled NO, PDE5 inhibitors, and recently sGC stimulators. The therapeutic armamentarium for many other disorders is expected in the near future. There are currently numerous active basic and clinical research programs in universities and industries attempting to develop novel therapies for many diseases and medical applications. PMID:27451093

  5. 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.

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

    PubMed

    Meng, Xiangpeng; Ryu, Jina; Kim, Bumsik; Ko, Sanghoon

    2016-07-01

    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

  7. 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

  8. Trichloroethylene oxidation by purified toluene 2-monooxygenase: products, kinetics, and turnover-dependent inactivation.

    PubMed Central

    Newman, L M; Wackett, L P

    1997-01-01

    Trichloroethylene is oxidized by several types of nonspecific bacterial oxygenases. Toluene 2-monooxygenase from Burkholderia cepacia G4 is implicated in trichloroethylene oxidation and is uniquely suggested to be resistant to turnover-dependent inactivation in vivo. In this work, the oxidation of trichloroethylene was studied with purified toluene 2-monooxygenase. All three purified toluene 2-monooxygenase protein components and NADH were required to reconstitute full trichloroethylene oxidation activity in vitro. The apparent Km and Vmax were 12 microM and 37 nmol per min per mg of hydroxylase component, respectively. Ten percent of the full activity was obtained when the small-molecular-weight enzyme component was omitted. The stable oxidation products, accounting for 84% of the trichloroethylene oxidized, were carbon monoxide, formic acid, glyoxylic acid, and covalently modified oxygenase proteins that constituted 12% of the reacted [14C]trichloroethylene. The stable oxidation products may all derive from the unstable intermediate trichloroethylene epoxide that was trapped by reaction with 4-(p-nitrobenzyl)pyridine. Chloral hydrate and dichloroacetic acid were not detected. This finding differs from that with soluble methane monooxygenase and cytochrome P-450 monooxygenase, which produce chloral hydrate. Trichloroethylene-dependent inactivation of toluene 2-monooxygenase activity was observed. All of the protein components were covalently modified during the oxidation of trichloroethylene. The addition of cysteine to reaction mixtures partially protected the enzyme system against inactivation, most notably protecting the NADH-oxidoreductase component. This suggested the participation of diffusible intermediates in the inactivation of the oxidoreductase. PMID:8981984

  9. Temperature dependent optical properties of pentacene films on zinc oxide

    SciTech Connect

    Helzel, J.; Jankowski, S.; El Helou, M.; Witte, G.; Heimbrodt, W.

    2011-11-21

    The optical transitions of pentacene films deposited on ZnO have been studied by absorption spectroscopy as a function of temperature in the range of room temperature down to 10 K. The pentacene films were prepared with thicknesses of 10 nm, 20 nm, and 100 nm on the ZnO-O(000-1) surface by molecular beam deposition. A unique temperature dependence has been observed for the two Davydov components of the excitons for different film thicknesses. At room temperature, the energetic positions of the respective absorption bands are the same for all films, whereas the positions differ more than 20 meV at 10 K caused by the very different expansion coefficients of pentacene and ZnO. Although the pentacene is just bonded via van der Waals interaction to the ZnO substrate, the very first pentacene monolayer (adlayer) is forced to keep the initial position on the ZnO surface and suffering, therefore, a substantial tensile strain. For all the subsequent pentacene monolayers, the strain is reduced step by step resulting electronically in a strong potential gradient at the interface.

  10. 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.

  11. Chemolithotrophic nitrate-dependent Fe(II)-oxidizing nature of actinobacterial subdivision lineage TM3

    PubMed Central

    Kanaparthi, Dheeraj; Pommerenke, Bianca; Casper, Peter; Dumont, Marc G

    2013-01-01

    Anaerobic nitrate-dependent Fe(II) oxidation is widespread in various environments and is known to be performed by both heterotrophic and autotrophic microorganisms. Although Fe(II) oxidation is predominantly biological under acidic conditions, to date most of the studies on nitrate-dependent Fe(II) oxidation were from environments of circumneutral pH. The present study was conducted in Lake Grosse Fuchskuhle, a moderately acidic ecosystem receiving humic acids from an adjacent bog, with the objective of identifying, characterizing and enumerating the microorganisms responsible for this process. The incubations of sediment under chemolithotrophic nitrate-dependent Fe(II)-oxidizing conditions have shown the enrichment of TM3 group of uncultured Actinobacteria. A time-course experiment done on these Actinobacteria showed a consumption of Fe(II) and nitrate in accordance with the expected stoichiometry (1:0.2) required for nitrate-dependent Fe(II) oxidation. Quantifications done by most probable number showed the presence of 1 × 104 autotrophic and 1 × 107 heterotrophic nitrate-dependent Fe(II) oxidizers per gram fresh weight of sediment. The analysis of microbial community by 16S rRNA gene amplicon pyrosequencing showed that these actinobacterial sequences correspond to ∼0.6% of bacterial 16S rRNA gene sequences. Stable isotope probing using 13CO2 was performed with the lake sediment and showed labeling of these Actinobacteria. This indicated that they might be important autotrophs in this environment. Although these Actinobacteria are not dominant members of the sediment microbial community, they could be of functional significance due to their contribution to the regeneration of Fe(III), which has a critical role as an electron acceptor for anaerobic microorganisms mineralizing sediment organic matter. To the best of our knowledge this is the first study to show the autotrophic nitrate-dependent Fe(II)-oxidizing nature of TM3 group of uncultured Actinobacteria

  12. Dissolution of amorphous Ti-Zr-Si alloy during anodic oxidation with formation of barrier films

    SciTech Connect

    Isaev, N.I.; Yakovlev, V.B.; Iovdal'skii, A.A.; Gorshkov, T.P.

    1988-07-01

    Radiometric analysis of a solution has been used to study kinetic mechanisms for dissolution of amorphous alloy components in acid aqueous solutions with anodic oxidation in different regimes. In a galvanostatic regime for alloy and crystalline Ti, Zr, and Ta two sections are detected: an initial section of accelerated dissolution and a steady section. An increase in dissolution of zirconium from the alloy has been revealed compared with pure crystalline zirconium. Potentiostatic oxidation is accompanied by a slowdown in dissolution similar to a change in current. Current yield has been analyzed for dissolution of the main elements and nonrectifying impurities of the alloy (for example copper). Gamma spectroscopy using the gamma radiation from neutron-activated isotopes of the components and impurities was performed.

  13. Composition dependence of the photochemical reduction of Ag+ by as-grown Pb(ZrxTi1-x)O3 films on indium tin oxide electrode

    NASA Astrophysics Data System (ADS)

    Zhang, Man; Jiang, Chunxiang; Dong, Wen; Zheng, Fengang; Fang, Liang; Su, Xiaodong; Shen, Mingrong

    2013-09-01

    Photochemical growth of metal particles on ferroelectric films has usually been found to depend on polarization effect solely. This research exploits the interplay of the film/electrode interface barrier and depolarization field on the photoreduction of Ag+ to Ag onto Pb(Zr,Ti)O3 (PZT) films deposited on indium tin oxide (ITO) electrodes. Ag nanoparticles are observed on the as-grown polycrystalline PZT films without poling, while the particle size and density are closely related to the concentration of Zr in PZT and the poling direction. The enhancement on the photoelectrochemical properties of the ITO/PZT photocathode by the decoration of Ag nanoparticles is finally demonstrated.

  14. Anaerobic, Nitrate-Dependent Fe(II) Oxidation Under Advective Flow

    NASA Astrophysics Data System (ADS)

    Weber, K. A.; Coates, J. D.

    2005-12-01

    Microbially-catalyzed nitrate-dependent Fe(II) oxidation has been identified as a ubiquitous biogeochemical process contributing to anaerobic iron redox cycling in sedimentary environments. Most probable number enumeration revealed nitrate-dependent Fe(II) oxidizing microbial communities in groundwater and subsurface sediments in the order of 0 - 2.04 x 103 cells mL-1 and 2.39 x 102 - 1.17 x 103 cells (g wet sediment)-1, respectively. The efficacy of nitrate-dependent Fe(II) oxidation under advective flow was evaluated in a meso-scale column reactor packed with sterile low iron sand amended with subsurface sediments collected from the NABIR FRC background field site (10% mass/mass). Continuous flow of minimal medium mimicked the natural groundwater. Periodic FeCl2 and nitrate injections over a period of 49 days resulted in the retention of 95% of the iron (290 mmol). Extraction of solid-phase Fe revealed a net increase in Fe(III) of 160 mmol above background Fe(III) content indicating that 55% of the injected Fe(II) was oxidized. Differential solubility analysis of 0.5M HCl-extractable Fe and 3M HCl-extractable Fe indicated that the oxidation product was crystalline in nature as only 20% was soluble in 0.5M HCl. This formation of crystalline biogenic Fe(III) oxides is consistent with previous studies. Periodic injections of nitrate and acetate did not result in significant changes in Fe(II) or Fe(III) throughout a control column. Together these results demonstrate that native subsurface sediments harbor microbial communities capable of nitrate-dependent Fe(II) oxidation under advective flow. The biogenic formation of reactive Fe(III) oxide minerals capable of immobilizing heavy metals and radionuclides presents a plausible bioremediative strategy for contaminated subsurface environments.

  15. Oxidative and pro-inflammatory impact of regular and denicotinized cigarettes on blood brain barrier endothelial cells: is smoking reduced or nicotine-free products really safe?

    PubMed Central

    2014-01-01

    Background Both active and passive tobacco smoke (TS) potentially impair the vascular endothelial function in a causative and dose-dependent manner, largely related to the content of reactive oxygen species (ROS), nicotine, and pro-inflammatory activity. Together these factors can compromise the restrictive properties of the blood–brain barrier (BBB) and trigger the pathogenesis/progression of several neurological disorders including silent cerebral infarction, stroke, multiple sclerosis and Alzheimer’s disease. Based on these premises, we analyzed and assessed the toxic impact of smoke extract from a range of tobacco products (with varying levels of nicotine) on brain microvascular endothelial cell line (hCMEC/D3), a well characterized human BBB model. Results Initial profiling of TS showed a significant release of reactive oxygen (ROS) and reactive nitrogen species (RNS) in full flavor, nicotine-free (NF, “reduced-exposure” brand) and ultralow nicotine products. This release correlated with increased oxidative cell damage. In parallel, membrane expression of endothelial tight junction proteins ZO-1 and occludin were significantly down-regulated suggesting the impairment of barrier function. Expression of VE-cadherin and claudin-5 were also increased by the ultralow or nicotine free tobacco smoke extract. TS extract from these cigarettes also induced an inflammatory response in BBB ECs as demonstrated by increased IL-6 and MMP-2 levels and up-regulation of vascular adhesion molecules, such as VCAM-1 and PECAM-1. Conclusions In summary, our results indicate that NF and ultralow nicotine cigarettes are potentially more harmful to the BBB endothelium than regular tobacco products. In addition, this study demonstrates that the TS-induced toxicity at BBB ECs is strongly correlated to the TAR and NO levels in the cigarettes rather than the nicotine content. PMID:24755281

  16. Evaluation of the energy barrier for failure of Au atomic contact based on temperature dependent current-voltage characteristics.

    PubMed

    Aiba, Akira; Kaneko, Satoshi; Fujii, Shintaro; Nishino, Tomoaki; Kiguchi, Manabu

    2016-08-01

    We investigated the mechanical stability of single gold atomic contacts at an applied bias voltage of 0-1 V using a nano-fabricated mechanically controllable break junction technique at 300-400 K under ambient conditions. The single atomic contact shows the quantized conductance (G0 = 2e(2)/h) and can carry considerably large current, which results in the current-induced failure of the contact. The contact failure behaviour under the applied bias conditions was studied by statistical analysis of the current-voltage (I-V) curves of the single Au contacts. We demonstrated that, at the elevated temperature of 300-400 K, the current-induced local heating effect is negligibly small and current-induced forces in the contact are responsible for the observed failure of the single gold contacts under the high bias voltage conditions (>0.4 V). Furthermore, based on the temperature dependence of the contact failure behaviour in the I-V curves, the energy barrier of the contact-failure was evaluated to be ca. 0.1 V. PMID:27427285

  17. Vulnerability of the retinal microvasculature to oxidative stress: ion channel-dependent mechanisms.

    PubMed

    Fukumoto, Masanori; Nakaizumi, Atsuko; Zhang, Ting; Lentz, Stephen I; Shibata, Maho; Puro, Donald G

    2012-05-01

    Although oxidative stress is a hallmark of important vascular disorders such as diabetic retinopathy, it remains unclear why the retinal microvasculature is particularly vulnerable to this pathophysiological condition. We postulated that redox-sensitive ion channels may play a role. Using H(2)O(2) to cause oxidative stress in microvascular complexes freshly isolated from the adult rat retina, we assessed ionic currents, cell viability, intracellular oxidants, and cell calcium by using perforated-patch recordings, trypan blue dye exclusion, and fura-2 fluorescence, respectively. Supporting a role for the oxidant-sensitive ATP-sensitive K (K(ATP)) channels, we found that these channels are activated during exposure of retinal microvessels to H(2)O(2). Furthermore, their inhibition by glibenclamide significantly lessened H(2)O(2)-induced microvascular cell death. Additional experiments established that by increasing the influx of calcium into microvascular cells, the K(ATP) channel-mediated hyperpolarization boosted the vulnerability of these cells to oxidative stress. In addition to the K(ATP) channel-dependent mechanism for increasing the lethality of oxidative stress, we also found that the vulnerability of cells in the capillaries, but not in the arterioles, was further boosted by a K(ATP) channel-independent mechanism, which our experiments indicated involves the oxidant-induced activation of calcium-permeable nonspecific cation channels. Taken together, our findings support a working model in which both K(ATP) channel-independent and K(ATP) channel-dependent mechanisms render the capillaries of the retina particularly vulnerable to oxidative stress. Identification of these previously unappreciated mechanisms for boosting the lethality of oxidants may provide new targets for pharmacologically limiting damage to the retinal microvasculature during periods of oxidative stress. PMID:22345512

  18. 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.

  19. 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.

  20. 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.

  1. Polyinosinic:polycytidylic acid induces protein kinase D–dependent disassembly of apical junctions and barrier dysfunction in airway epithelial cells

    PubMed Central

    Rezaee, Fariba; Meednu, Nida; Emo, Jason A.; Saatian, Bahman; Chapman, Timothy J.; Naydenov, Nayden G.; De Benedetto, Anna; Beck, Lisa A.; Ivanov, Andrei I.; Georas, Steve N.

    2011-01-01

    Background Disruption of the epithelial barrier might be a risk factor for allergen sensitization and asthma. Viral respiratory tract infections are strongly associated with asthma exacerbation, but the effects of respiratory viruses on airway epithelial barrier function are not well understood. Many viruses generate double-stranded RNA, which can lead to airway inflammation and initiate an antiviral immune response. Objectives We investigated the effects of the synthetic double-stranded RNA polyinosinic:polycytidylic acid (polyI:C) on the structure and function of the airway epithelial barrier in vitro. Methods 16HBE14o- human bronchial epithelial cells and primary airway epithelial cells at an air-liquid interface were grown to confluence on Transwell inserts and exposed to polyI:C. We studied epithelial barrier function by measuring transepithelial electrical resistance and paracellular flux of fluorescent markers and structure of epithelial apical junctions by means of immunofluorescence microscopy. Results PolyI:C induced a profound decrease in transepithelial electrical resistance and increase in paracellular permeability. Immunofluorescence microscopy revealed markedly reduced junctional localization of zonula occludens-1, occludin, E-cadherin, β-catenin, and disorganization of junction-associated actin filaments. PolyI:C induced protein kinase D (PKD) phosphorylation, and a PKD antagonist attenuated polyI:C-induced disassembly of apical junctions and barrier dysfunction. Conclusions PolyI:C has a powerful and previously unsuspected disruptive effect on the airway epithelial barrier. PolyI:C-dependent barrier disruption is mediated by disassembly of epithelial apical junctions, which is dependent on PKD signaling. These findings suggest a new mechanism potentially underlying the associations between viral respiratory tract infections, airway inflammation, and allergen sensitization. PMID:21996340

  2. Oxidative cleavage of cellulose by fungal copper-dependent polysaccharide monooxygenases.

    PubMed

    Beeson, William T; Phillips, Christopher M; Cate, Jamie H D; Marletta, Michael A

    2012-01-18

    Fungal-derived, copper-dependent polysaccharide monooxygenases (PMOs), formerly known as GH61 proteins, have recently been shown to catalyze the O(2)-dependent oxidative cleavage of recalcitrant polysaccharides. Different PMOs isolated from Neurospora crassa were found to generate oxidized cellodextrins modified at the reducing or nonreducing ends upon incubation with cellulose and cellobiose dehydrogenase. Here we show that the nonreducing end product formed by an N. crassa PMO is a 4-ketoaldose. Together with isotope labeling experiments, further support is provided for a mechanism involving oxygen insertion and subsequent elimination to break glycosidic bonds in crystalline cellulose. PMID:22188218

  3. 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.

  4. 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

  5. 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

  6. 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

  7. Cerebral nitric oxide represses choroid plexus NFκB-dependent gateway activity for leukocyte trafficking

    PubMed Central

    Baruch, Kuti; Kertser, Alexander; Porat, Ziv; Schwartz, Michal

    2015-01-01

    Chronic neuroinflammation is evident in brain aging and neurodegenerative disorders and is often associated with excessive nitric oxide (NO) production within the central nervous system (CNS). Under such conditions, increased NO levels are observed at the choroid plexus (CP), an epithelial layer that forms the blood–cerebrospinal fluid barrier (BCSFB) and serves as a selective gateway for leukocyte entry to the CNS in homeostasis and following injury. Here, we hypothesized that elevated cerebral NO levels interfere with CP gateway activity. We found that induction of leukocyte trafficking determinants by the CP and sequential leukocyte entry to the CSF are dependent on the CP epithelial NFκB/p65 signaling pathway, which was inhibited upon exposure to NO. Examining the CP in 5XFAD transgenic mouse model of Alzheimer's disease (AD-Tg) revealed impaired ability to mount an NFκB/p65-dependent response. Systemic administration of an NO scavenger in AD-Tg mice alleviated NFκB/p65 suppression at the CP and augmented its gateway activity. Together, our findings identify cerebral NO as a negative regulator of CP gateway activity for immune cell trafficking to the CNS. PMID:25940071

  8. 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.

  9. 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.

  10. 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

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

    PubMed

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

    2015-01-01

    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 Mn (x) (+) 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 MnO x 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 MnO x species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnO x 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

  12. Study of polystyrene-poly(ethylene oxide) diblock copolymer monolayers as barriers to protein adsorption

    NASA Astrophysics Data System (ADS)

    Jogikalmath, Gangadhar

    Protein adsorption resistant surfaces find use in many biomedical applications, such as catheters, dialysis devices and biosensors that involve blood contacting surfaces. To ensure long-term functioning of a device in an environment containing protein, there is a need to produce homogeneous surfaces that are resistant to protein adsorption. A polymer brush covered surface, produced by either physical adsorption or chemical grafting of hydrophilic polymers to surfaces, is one of the approaches used in creating such surfaces. High grafting densities needed to make an effective barrier are usually not realized in chemical grafting/adsorption from solution, due to self-exclusion of surface grafted molecules. In this dissertation polymer brush surfaces formed by chemically grafted PEO molecules and transferred monolayers of PS-b-PEO diblock copolymers are investigated using atomic force microscopy (AFM), surface plasmon resonance (SPR) and surface pressure measurement techniques. An AFM adhesion mapping technique was used to evaluate the surface heterogeneity of chemically modified PEO and transferred diblock copolymer monolayer surfaces. The behavior of PS-b-PEO molecules at the air-water interface was studied using Langmuir trough. The stability of transferred diblock copolymer monolayers was investigated using AFM. Using SPR, protein adsorption to the diblock copolymer layers was investigated as a function of protein size (using HSA and ferritin) as a function of grafting density of PEO in the monolayer. It was seen that a lower density of the PS-b-PEO monolayer was sufficient to prevent ferritin adsorption (larger protein) while a higher density brush layer was required to achieve complete prevention of HSA adsorption to the surface. The effect of mobility of the polymer brush layer on protein adsorption prevention was analyzed using SPR and surface pressure measurements. It was seen that the copolymer monolayer (at the air-buffer interface) rearranged itself to

  13. Human immunodeficiency virus infection of human astrocytes disrupts blood-brain barrier integrity by a gap junction-dependent mechanism.

    PubMed

    Eugenin, Eliseo A; Clements, Janice E; Zink, M Christine; Berman, Joan W

    2011-06-29

    HIV infection of the CNS is an early event after primary infection, resulting in neurological complications in a significant number of individuals despite antiretroviral therapy (ART). The main cells infected with HIV within the CNS are macrophages/microglia and a small fraction of astrocytes. The role of these few infected astrocytes in the pathogenesis of neuroAIDS has not been examined extensively. Here, we demonstrate that few HIV-infected astrocytes (4.7 ± 2.8% in vitro and 8.2 ± 3.9% in vivo) compromise blood-brain barrier (BBB) integrity. This BBB disruption is due to endothelial apoptosis, misguided astrocyte end feet, and dysregulation of lipoxygenase/cyclooxygenase, BK(Ca) channels, and ATP receptor activation within astrocytes. All of these alterations in BBB integrity induced by a few HIV-infected astrocytes were gap junction dependent, as blocking these channels protected the BBB from HIV-infected astrocyte-mediated compromise. We also demonstrated apoptosis in vivo of BBB cells in contact with infected astrocytes using brain tissue sections from simian immunodeficiency virus-infected macaques as a model of neuroAIDS, suggesting an important role for these few infected astrocytes in the CNS damage seen with HIV infection. Our findings describe a novel mechanism of bystander BBB toxicity mediated by low numbers of HIV-infected astrocytes and amplified by gap junctions. This mechanism of toxicity contributes to understanding how CNS damage is spread even in the current ART era and how minimal or controlled HIV infection still results in cognitive impairment in a large population of infected individuals. PMID:21715610

  14. Silicon oxide barrier films deposited on PET foils in pulsed plasmas: influence of substrate bias on deposition process and film properties

    NASA Astrophysics Data System (ADS)

    Steves, S.; Ozkaya, B.; Liu, C.-N.; Ozcan, O.; Bibinov, N.; Grundmeier, G.; Awakowicz, P.

    2013-02-01

    A widely used plastic for packaging, polyethylene terephtalate (PET) offers limited barrier properties against gas permeation. For many applications of PET (from food packaging to micro electronics) improved barrier properties are essential. A silicon oxide barrier coating of PET foils is applied by means of a pulsed microwave driven low-pressure plasma. While the adjustment of the microwave power allows for a control of the ion production during the plasma pulse, a substrate bias controls the energy of ions impinging on the substrate. Detailed analysis of deposited films applying oxygen permeation measurements, x-ray photoelectron spectroscopy and atomic force microscopy are correlated with results from plasma diagnostics describing the deposition process. The influence of a change in process parameters such as gas mixture and substrate bias on the gas temperature, electron density, mean electron energy, ion energy and the atomic oxygen density is studied. An additional substrate bias results in an increase in atomic oxygen density up to a factor of 6, although plasma parameter such as electron density of ne = 3.8 ± 0.8 × 1017 m-3 and electron temperature of kBTe = 1.7 ± 0.1 eV are unmodified. It is shown that atomic oxygen densities measured during deposition process higher than nO = 1.8 × 1021 m-3 yield in barrier films with a barrier improvement factor up to 150. Good barrier films are highly cross-linked and show a smooth morphology.

  15. 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

    2015-06-01

    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. PMID:25959397

  16. 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. PMID:27474625

  17. Thickness-Dependent Charge Carrier Dynamics in CdSe/ZnSe/CdS Core/Barrier/Shell Nanoheterostructures.

    PubMed

    Yadav, Sushma; Chowdhury, Apurba; Sapra, Sameer

    2016-03-01

    We report the synthesis of CdSe/ZnSe/CdS heterostructures composed of type I and type II band alignments, where ZnSe acts as a barrier for charge carriers between the CdSe core and the CdS shell as well as being an active component of the type I (CdSe/ZnSe) and type II (ZnSe/CdS) structure simultaneously. We investigated the effect of the thickness of the barrier and the shell on the charge carrier dynamics by using UV/Vis absorbance, photoluminescence (PL), and time-resolved fluorescence techniques. The experimental data are supported by simple theoretical calculations based on effective mass approximation (EMA). PL results indicate the emission from both type I and type II structures. Time-resolved fluorescence studies show that the lifetime of the core emission decreases with increasing barrier width, owing to a greater confinement of the exciton to the core, whereas it increases with shell width because of the tunneling of charge carriers, primarily electrons, delaying the recombination of the exciton. The lifetime of the shell emission decreases with shell width as well as barrier width and height, with a larger effect being observed for the barrier width and negligible for the associated changes in the barrier height. PMID:26511899

  18. Nitric Oxide Protects against Infection-Induced Neuroinflammation by Preserving the Stability of the Blood-Brain Barrier

    PubMed Central

    Olivera, Gabriela C.; Ren, Xiaoyuan; Vodnala, Suman K.; Lu, Jun; Coppo, Lucia; Leepiyasakulchai, Chaniya; Holmgren, Arne; Kristensson, Krister; Rottenberg, Martin E.

    2016-01-01

    Nitric oxide (NO) generated by inducible NO synthase (iNOS) is critical for defense against intracellular pathogens but may mediate inflammatory tissue damage. To elucidate the role of iNOS in neuroinflammation, infections with encephalitogenic Trypanosoma brucei parasites were compared in inos-/- and wild-type mice. Inos-/- mice showed enhanced brain invasion by parasites and T cells, and elevated protein permeability of cerebral vessels, but similar parasitemia levels. Trypanosome infection stimulated T cell- and TNF-mediated iNOS expression in perivascular macrophages. NO nitrosylated and inactivated pro-inflammatory molecules such as NF-κΒp65, and reduced TNF expression and signalling. iNOS-derived NO hampered both TNF- and T cell-mediated parasite brain invasion. In inos-/- mice, TNF stimulated MMP, including MMP9 activity that increased cerebral vessel permeability. Thus, iNOS-generated NO by perivascular macrophages, strategically located at sites of leukocyte brain penetration, can serve as a negative feed-back regulator that prevents unlimited influx of inflammatory cells by restoring the integrity of the blood-brain barrier. PMID:26915097

  19. 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. PMID:25435001

  20. 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.

  1. MCNP-POLIMI Evaluation of Time Dependent Coincidence Between Detectors for Fissile Metal Vs. Oxide Determination

    SciTech Connect

    Pozzi, S. A.; Mihalczo, J. T.

    2002-06-03

    In the past, passive Nuclear Materials Identification System (NMIS) measurements on plutonium metal shells at VNIIEF have shown the sensitivity of the acquired covariance functions to shell mass and thickness for a variety of shell thicknesses from 6 to 30 mm and masses varying from 1829 to 4468g. The technique acquires the time-dependent coincidence distribution between plastic scintillators detecting radiation from the Pu. The measurements showed the sensitivity of the acquired signature to the different spontaneous emission, attenuation, and multiplication properties of the shells. In this work, the MCNP-POLIMI neutron and photon transport code was used to simulate passive measurements on plutonium metal and oxide. The code is a modified version of MCNP, which attempts to calculate more correctly quantities that depend on the second moment of the neutron and gamma distributions, and attempts to model detector pulses as closely as possible. MCNP-POLIMI, together with a post-processing code, can simulate all the time-dependent coincidence distributions measured by NMIS. In particular, the simulations evaluate the time-dependent coincidence distributions between detectors for plutonium samples having mass 2 and 4 kg, in metal and oxide form. This work shows that the time-dependent coincidence distributions between two scintillators measured by NMIS can be used to distinguish metal from oxide.

  2. Polarisation dependence of Schottky barrier heights at ferroelectric BaTiO3 / RuO2 interfaces: influence of substrate orientation and quality

    NASA Astrophysics Data System (ADS)

    Hubmann, Andreas H.; Li, Shunyi; Zhukov, Sergey; von Seggern, Heinz; Klein, Andreas

    2016-07-01

    In situ x-ray photoelectron spectroscopy was employed to examine the change in Schottky barrier height Δ {Φ\\text{B}} at BaTiO3/RuO2 interfaces upon polarisation reversal for [1 0 0], [1 1 0] and [1 1 1] oriented BaTiO3 single crystals. Compared to previous measurements on BaTiO3/RuO2 interfaces (Chen and Klein 2012 Phys. Rev. B 86 094105), the crystals exhibit a significantly reduced dependence of barrier height on polarisation direction. This is connected to a much higher polarisation of the present cystals, which is comparable to the accepted bulk polarisation of BaTiO3 of 26~μ \\text{C}~\\text{c}{{\\text{m}}-2} and which exhibit the expected dependence on crystal orientation. This indicates a much higher crystal quality in the present experiments, which is also confirmed by a Kolmogorov–Avrami–Ishibashi like polarisation switching dynamics. It is observed that Δ {Φ\\text{B}} is reduced for the [1 1 0] and [1 1 1] orientation and scales with polarisation as long as crystals from the same batch are used. The fact, that a poor polarisation hysteresis behaviour relates to a high polarisation dependence of Schottky barrier height, indicates that the electrode’s ability to screen ferroelectric polarisation charges depends sensitively on crystal and/or interface quality.

  3. 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.

  4. Redox-dependent regulation, redox control and oxidative damage in plant cells subjected to abiotic stress.

    PubMed

    Dietz, Karl-Josef

    2010-01-01

    Stress development intricately involves uncontrolled redox reactions and oxidative damage to functional macromolecules. Three phases characterize progressing abiotic stress and the stress strength; in the first phase redox-dependent deregulation in metabolism, in the second phase detectable development of oxidative damage and in the third phase cell death. Each phase is characterized by traceable biochemical features and specific molecular responses that reflect on the one hand cell damage but on the other hand indicate specific regulation and redox signalling aiming at compensation of stress impact. PMID:20387040

  5. When Free Is Not for Me: Confronting the Barriers to Use of Free Quitline Telephone Counseling for Tobacco Dependence

    PubMed Central

    Sheffer, Christine; Brackman, Sharon; Lercara, Charnette; Cottoms, Naomi; Olson, Mary; Panissidi, Luana; Pittman, Jami; Stayna, Helen

    2015-01-01

    Remarkable disparities in smoking rates in the United States contribute significantly to socioeconomic and minority health disparities. Access to treatment for tobacco use can help address these disparities, but quitlines, our most ubiquitous treatment resource, reach just 1%–2% of smokers. We used community-based participatory methods to develop a survey instrument to assess barriers to use of the quitline in the Arkansas Mississippi delta. Barriers were quitline specific and barriers to cessation more broadly. Over one-third (34.9%) of respondents (n = 799) did not have access to a telephone that they could use for the quitline. Respondents reported low levels of knowledge about the quitline, quitting, and trust in tobacco treatment programs as well as considerable ambivalence about quitting including significant concerns about getting sick if they quit and strong faith-based beliefs about quitting. These findings suggest quitlines are not accessible to all lower socioeconomic groups and that significant barriers to use include barriers to cessation. These findings suggest targets for providing accessible tobacco use treatment services and addressing concerns about cessation among lower income, ethnic minority, and rural groups. PMID:26703662

  6. When Free Is Not for Me: Confronting the Barriers to Use of Free Quitline Telephone Counseling for Tobacco Dependence.

    PubMed

    Sheffer, Christine; Brackman, Sharon; Lercara, Charnette; Cottoms, Naomi; Olson, Mary; Panissidi, Luana; Pittman, Jami; Stayna, Helen

    2016-01-01

    Remarkable disparities in smoking rates in the United States contribute significantly to socioeconomic and minority health disparities. Access to treatment for tobacco use can help address these disparities, but quitlines, our most ubiquitous treatment resource, reach just 1%-2% of smokers. We used community-based participatory methods to develop a survey instrument to assess barriers to use of the quitline in the Arkansas Mississippi delta. Barriers were quitline specific and barriers to cessation more broadly. Over one-third (34.9%) of respondents (n = 799) did not have access to a telephone that they could use for the quitline. Respondents reported low levels of knowledge about the quitline, quitting, and trust in tobacco treatment programs as well as considerable ambivalence about quitting including significant concerns about getting sick if they quit and strong faith-based beliefs about quitting. These findings suggest quitlines are not accessible to all lower socioeconomic groups and that significant barriers to use include barriers to cessation. These findings suggest targets for providing accessible tobacco use treatment services and addressing concerns about cessation among lower income, ethnic minority, and rural groups. PMID:26703662

  7. 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. PMID:26582023

  8. 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

  9. 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

  10. 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

    2016-01-01

    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. Age-dependence of free radical-induced oxidative damage in ischemic-reperfused rat heart.

    PubMed

    Nagy, K; Takács, I E; Pankucsi, C

    1996-01-01

    Oxygen free radical-induced oxidative damage is involved in both aging and ischemia-reperfusion. The purpose of this study was to determine the aging-induced oxidative alterations in rat heart as well as the age-dependence of heart injury following ischemia-reperfusion. A comparative study was performed on young and old ischemic-reperfused rat hearts. Protein oxidation and the ascorbyl radical level in heart tissue were determined in order to characterize the oxidative stress. Comparing the control conditions, old hearts have 31% more oxidized proteins as measured by protein carbonyl content, and 18% lower ascorbyl radical level as determined by ESR, than young ones. The extent of increase of protein oxidation and ascorbyl free radical depletion induced by ischemia-reperfusion is less pronounced in the old hearts (7 and 8% respectively), as compared to the young ones (55 and 21% respectively). Pre-treatment with a free radical scavenger, such as centrophenoxine, diminished the ischemia-reperfusion injury in both young and old rat hearts. PMID:15374178

  12. 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

  13. Annealing dependence of diamond-metal Schottky barrier heights probed by hard x-ray photoelectron spectroscopy

    SciTech Connect

    Gaowei, M.; Muller, E. M.; Rumaiz, A. K.; Weiland, C.; Cockayne, E.; Woicik, J. C.; Jordan-Sweet, J.; Smedley, J.

    2012-05-14

    Hard x-ray photoelectron spectroscopy was applied to investigate the diamond-metal Schottky barrier heights for several metals and diamond surface terminations. The position of the diamond valence-band maximum was determined by theoretically calculating the diamond density of states and applying cross section corrections. The diamond-platinum Schottky barrier height was lowered by 0.2 eV after thermal annealing, indicating annealing may increase carrier injection in diamond devices leading to photoconductive gain. The platinum contacts on oxygen-terminated diamond was found to provide a higher Schottky barrier and therefore a better blocking contact than that of the silver contact in diamond-based electronic devices.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Draft Genome Sequence of a Potential Nitrate-Dependent Fe(II)-Oxidizing Bacterium, Aquabacterium parvum B6

    PubMed Central

    Zhang, Xiaoxin

    2016-01-01

    Aquabacterium parvum B6 is a potential nitrate-dependent Fe(II)-oxidizing bacterium. The genes related to its denitrifying mechanism and iron metabolisms were unknown. We present the draft genome of Aquabacterium parvum B6, which could provide further insight into the nitrate-dependent Fe(II)-oxidizing mechanism of strain B6. PMID:26823591

  19. Draft Genome Sequence of a Potential Nitrate-Dependent Fe(II)-Oxidizing Bacterium, Aquabacterium parvum B6.

    PubMed

    Zhang, Xiaoxin; Ma, Fang; Szewzyk, Ulrich

    2016-01-01

    Aquabacterium parvum B6 is a potential nitrate-dependent Fe(II)-oxidizing bacterium. The genes related to its denitrifying mechanism and iron metabolisms were unknown. We present the draft genome of Aquabacterium parvum B6, which could provide further insight into the nitrate-dependent Fe(II)-oxidizing mechanism of strain B6. PMID:26823591

  20. 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.

  1. Link between Cancer and Alzheimer Disease via Oxidative Stress Induced by Nitric Oxide-Dependent Mitochondrial DNA Overproliferation and Deletion

    PubMed Central

    Obrenovich, Mark E.; Tabrez, Shams; Jabir, Nasimudeen R.; Reddy, V. Prakash; Li, Yi; Burnstock, Geoffrey; Cacabelos, Ramon; Kamal, Mohammad Amjad

    2013-01-01

    Nitric oxide- (NO-) dependent oxidative stress results in mitochondrial ultrastructural alterations and DNA damage in cases of Alzheimer disease (AD). However, little is known about these pathways in human cancers, especially during the development as well as the progression of primary brain tumors and metastatic colorectal cancer. One of the key features of tumors is the deficiency in tissue energy that accompanies mitochondrial lesions and formation of the hypoxic smaller sized mitochondria with ultrastructural abnormalities. We speculate that mitochondrial involvement may play a significant role in the etiopathogenesis of cancer. Recent studies also demonstrate a potential link between AD and cancer, and anticancer drugs are being explored for the inhibition of AD-like pathology in transgenic mice. Severity of the cancer growth, metastasis, and brain pathology in AD (in animal models that mimic human AD) correlate with the degree of mitochondrial ultrastructural abnormalities. Recent advances in the cell-cycle reentry of the terminally differentiated neuronal cells indicate that NO-dependent mitochondrial abnormal activities and mitotic cell division are not the only important pathogenic factors in pathogenesis of cancer and AD, but open a new window for the development of novel treatment strategies for these devastating diseases. PMID:23691268

  2. Keap1 redox-dependent regulation of doxorubicin-induced oxidative stress response in cardiac myoblasts.

    PubMed

    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. PMID:24211725

  3. 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

  4. NRF2 Oxidative Stress Induced by Heavy Metals is Cell Type Dependent

    PubMed Central

    Simmons, Steven O; Fan, Chun-Yang; Yeoman, Kim; Wakefield, John; Ramabhadran, Ram

    2011-01-01

    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 study, we describe the development of an Nrf2-specific reporter gene assay that can be used to study the oxidative stress response in multiple cell types. Using five different cell lines, the Nrf2-activating potency of twenty metals was assessed across a range of concentrations. While ten of the metals tested (cadmium, cobalt, copper, gold, iron, lead, mercury, silver, sodium arsenite and zinc) stimulated Nrf2-dependent transcriptional activity in at least three of the engineered cell lines, only three (cadmium, copper and sodium arsenite) were active in all five cell lines. A comparison of metal-induced Nrf2 transcriptional activation revealed significant differences in the absolute magnitude of activation as well as the relative potencies between the cell lines tested. However, there was no direct correlation between activity and potency. Taken together, these results show that the capacity to stimulate Nrf2 activity and relative potencies of these test compounds are highly dependent on the cell type tested. Since oxidative stress is thought to be involved in the mode of action of many toxicological studies, this observation may inform the design of paradigms for toxicity testing for toxicant prioritization and characterization. PMID:21643505

  5. Precious metal oxides for electrochemical energy converters: Pseudocapacitance and pH dependence of redox processes

    NASA Astrophysics Data System (ADS)

    Kurzweil, P.

    The mechanism of charge storage in hydrous platinum metal oxides is considered in more detail with respect to the pH dependence of redox capacitance for applications in double-layer capacitors, fuel cells, and pH sensors. An amorphous RuO 2 electrode is able to work like a pH glass electrode during the titration of hydrochloric acid with sodium hydroxide solution. It is shown that the proton exchange mechanism at a glass membrane can be reproduced by platinum metal oxide-hydrates bound in a polymer matrix. Hydrous RuO 2, obtained by alkaline precipitation or thermal decomposition from RuCl 3, as well as single crystal RuO 2, were characterized by TOF-SIMS, NMR spectroscopy, and electrochemical techniques. The proton conductivity of hydrous RuO 2 appears to be due to the dissociative adsorption of water and the formation of acidic OH groups in Ru(III,IV) cluster ions. Depending on the pH of the solution, the electrode potential is determined by the formal hydrogen oxidation or oxygen reduction in ruthenium cluster ions. During aging, the active Ru(III) surface sites are partially oxidized to Ru(IV).

  6. 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

    2013-06-01

    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. PMID:23583694

  7. 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.

  8. Solvent-dependent oxidative coupling of 1-aryl-1,3-dicarbonyls and styrene.

    PubMed

    Casey, Brian M; Eakin, Cynthia A; Jiao, Jingliang; Sadasivam, Dhandapani V; Flowers, Robert A

    2009-12-26

    This report describes the scope and mechanism of the solvent-dependent, chemoselective oxidative coupling of 1-aryl-1,3-dicarbonyls with styrene using Ce(IV) reagents. Dihydrofuran derivatives are obtained when reactions are performed in methanol whereas alpha-tetralones can be selectively synthesized in acetonitrile and methylene chloride. Mechanistic studies are consistent with the rate of solvent-assisted deprotonation of a radical cation intermediate playing an integral role in the selective formation of products. PMID:20625455

  9. Corrigendum to Solvent-dependent oxidative coupling of 1-aryl-1,3-dicarbonyls and styrene.

    PubMed

    Casey, Brian M; Eakin, Cynthia A; Jiao, Jingliang; Sadasivam, Dhandapani V; Flowers, Robert A

    2010-07-24

    This report describes the scope and mechanism of the solvent-dependent, chemoselective oxidative coupling of 1-aryl-1,3-dicarbonyls with styrene using Ce(IV) reagents. Dihydrofuran derivatives are obtained when reactions are performed in methanol whereas nitrate esters can be selectively synthesized in acetonitrile and methylene chloride. Mechanistic studies are consistent with the rate of solvent-assisted deprotonation of a radical cation intermediate playing an integral role in the selective formation of products. PMID:20806051

  10. A transition in mechanisms of size dependent electrical transport at nanoscale metal-oxide interfaces

    SciTech Connect

    Hou, Jiechang; Nonnenmann, Stephen S.; Qin, Wei; Bonnell, Dawn A.

    2013-12-16

    As device miniaturization approaches nanoscale dimensions, interfaces begin to dominate electrical properties. Here the system archetype Au/SrTiO{sub 3} is used to examine the origin of size dependent transport properties along metal-oxide interfaces. We demonstrate that a transition between two classes of size dependent electronic transport mechanisms exists, defined by a critical size ε. At sizes larger than ε an edge-related tunneling effect proportional to 1/D (the height of the supported Au nanoparticle) is observed; interfaces with sizes smaller than ε exhibit random fluctuations in current. The ability to distinguish between these mechanisms is important to future developments in nanoscale device design.

  11. Investigation of Thickness Dependence of Metal Layer in Al/Mo/4H-SiC Schottky Barrier Diodes.

    PubMed

    Lee, Seula; Lee, Jinseon; Kang, Tai-Young; Kyoung, Sinsu; Jung, Eun Sik; Kim, Kyung Hwan

    2015-11-01

    In this paper, we present the preparation and characterization of Schottky barrier diodes based on silicon carbide with various Schottky metal layer thickness values. In this structure, molybdenum and aluminum were employed as the Schottky barrier metal and top electrode, respectively. Schottky metal layers were deposited with thicknesses ranging from 1000 to 3000 Å, and top electrodes were deposited with thickness as much as 3000 Å. The deposition of both metal layers was performed using the facing target sputtering (FTS) method, and the fabricated samples were annealed with the tubular furnace at 300 degrees C under argon ambient for 10 min. The Schottky barrier height, series resistance, and ideality factor was calculated from the forward I-V characteristic curve using the methods proposed by Cheung and Cheung, and by Norde. For as-deposited Schottky diodes, we observed an increase of the threshold voltage (V(T)) as the thickness of the Schottky metal layer increased. After the annealing, the Schottky barrier heights (SBHs) of the diodes, including Schottky metal layers of over 2000 Å, increased. In the case of the Schottky metal layer deposited to 1000 Å, the barrier heights decreased due to the annealing process. This may have been caused by the interfacial penetration phenomenon through the Schottky metal layer. For variations of V(T), the SBH changed with a similar tendency. The ideality factor and series resistance showed no significant changes before or after annealing. This indicates that this annealing condition is appropriate for Mo SiC structures. Our results confirm that it is possible to control V(T) by adjusting the thickness of the Schottky metal layer. PMID:26726688

  12. Evidence for oxidation-state-dependent conformational changes in human ferredoxin from multinuclear, multidimensional NMR spectroscopy.

    PubMed

    Xia, B; Volkman, B F; Markley, J L

    1998-03-17

    Human ferredoxin belongs to the vertebrate ferredoxin family which includes bovine adrenodoxin. It is a small (13.8 kDa) acidic protein with a [2Fe-2S] cluster. It functions as an electron shuttle in the cholesterol side-chain cleavage reaction which is the first step of steroid hormone biosynthesis. The protein studied here was produced in Escherichia coli and doubly labeled with 13C and 15N. The diamagnetic 15N, 13C', 13C alpha, 13C beta, 1H alpha, and 1HN resonances from about 70% of the 124 amino acid residues for oxidized human ferredoxin and 80% of those for the reduced protein have been assigned primarily on the basis of results from three-dimensional, triple-resonance experiments. Secondary structure features for human ferredoxin in its oxidized and reduced states have been identified from a combination of chemical shift index and NOE data. Comparison of NMR results from the protein in its oxidized and reduced states indicates that structural changes accompany the change in the oxidation state of the [2Fe-2S] cluster. Major differences are localized at two regions: residues 29-31 and residues 109-124; the latter stretch forms the C-terminal region of the protein. The possible functional significance of these oxidation-state-dependent structural changes is discussed. PMID:9521718

  13. Size-dependent nanoscale kirkendall effect during the oxidation of nickel nanoparticles.

    PubMed

    Railsback, Justin G; Johnston-Peck, Aaron C; Wang, Junwei; Tracy, Joseph B

    2010-04-27

    The transformation of Ni nanoparticles (NPs) of different sizes (average diameters of 9, 26, and 96 nm) during oxidation to hollow (single void) or porous (multiple voids) NiO through the nanoscale Kirkendall effect was observed by transmission electron microscopy. Samples treated for 1-4 h at 200-500 degrees C show that the structures of the completely oxidized NPs do not depend on the temperature, but oxidation proceeds more quickly at elevated temperatures. For the Ni/NiO system, after formation of an initial NiO shell (of thickness approximately 3 nm), single or multiple voids nucleate on the inner surface of the NiO shell, and the voids grow until conversion to NiO is complete. Differences in the void formation and growth processes cause size-dependent nanostructural evolution: For 9 and 26 nm NPs, a single void forms beneath the NiO shell, and the void grows by moving across the NP while conversion to NiO occurs opposite the site where the void initially formed. Because of the differences in the Ni/NiO volume ratios for the 9 and 26 nm NPs when the void first forms, they have distinct nanostructures: The 9 nm NPs form NiO shells that are nearly radially symmetric, while there is a pronounced asymmetry in the NiO shells for 26 nm NPs. By choosing an intermediate oxidation temperature and varying the reaction time, partially oxidized Ni(core)/NiO(shell) NPs can be synthesized with good control. For 96 nm NPs, multiple voids form and grow, which results in porous NiO NPs. PMID:20361781

  14. Temperature dependence of the inhomogeneous parameters of the Mo/4H–SiC Schottky barrier diodes

    NASA Astrophysics Data System (ADS)

    Latreche, A.; Ouennoughi, Z.; Weiss, R.

    2016-08-01

    The inhomogeneous parameters of Mo/4H–SiC Schottky barrier diodes were determined from current–voltage (I–V) characteristics in the temperature range of 303–498 K by using a general approach for the real Schottky diode. In this approach the total series resistances is divided into two resistances; the first one (R P) is the sum of the series resistances (r) of the particular diodes connected in parallel and the second is the common resistance (R C) to all particular diodes. The mean barrier height (\\bar{φ }) and the standard deviation (σ) decrease linearly with decreasing temperature and they are between the values for the diodes with the two limiting cases; no current spreading and full current spreading. The series resistance R C increases, while the series resistance R P slightly decreases with decreasing temperature.

  15. Dependence of the 0.7 anomaly on the curvature of the potential barrier in quantum wires

    NASA Astrophysics Data System (ADS)

    Smith, L. W.; Al-Taie, H.; Lesage, A. A. J.; Sfigakis, F.; See, P.; Griffiths, J. P.; Beere, H. E.; Jones, G. A. C.; Ritchie, D. A.; Hamilton, A. R.; Kelly, M. J.; Smith, C. G.

    2015-06-01

    Ninety-eight one-dimensional channels defined using split gates fabricated on a GaAs/AlGaAs heterostructure are measured during one cooldown at 1.4 K. The devices are arranged in an array on a single chip and are individually addressed using a multiplexing technique. The anomalous conductance feature known as the "0.7 structure" is studied using statistical techniques. The ensemble of data shows that the 0.7 anomaly becomes more pronounced and occurs at lower values as the curvature of the potential barrier in the transport direction decreases. This corresponds to an increase in the effective length of the device. The 0.7 anomaly is not strongly influenced by other properties of the conductance related to density. The curvature of the potential barrier appears to be the primary factor governing the shape of the 0.7 structure at a given T and B .

  16. Volatility and oxidative aging of aqueous maleic acid aerosol droplets and the dependence on relative humidity.

    PubMed

    Dennis-Smither, Benjamin J; Marshall, Frances H; Miles, Rachael E H; Preston, Thomas C; Reid, Jonathan P

    2014-07-31

    The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapor pressure determined to be (1.7 ± 0.2) × 10(-3) Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the subcooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size, and refractive index have been made during ozonolysis at RHs in the range 50-80%, providing insight into the volatility of organic products, changes in the droplet hygroscopicity, and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al. ( J. Geophys. Res. 2011 , 116 , D15204 ). Once oxidized, particles are shown to form amorphous phases on drying rather than crystallization, with slow evaporation kinetics of residual water. PMID:25003240

  17. Induction of Size-Dependent Breakdown of Blood-Milk Barrier in Lactating Mice by TiO2 Nanoparticles

    PubMed Central

    Wu, Ling; Bai, Yuhong; Jia, Jianbo; Zhang, Yi; Zhang, Bin; Yan, Bing

    2015-01-01

    This study aims to investigate the potential nanotoxic effects of TiO2 nanoparticles (TNPs) to dams and pups during lactation period. TiO2 nanoparticles are accumulated in mammary glands of lactating mice after i.v. administration. This accumulation of TiO2 NP likely causes a ROS-induced disruption of tight junction of the blood-milk barrier as indicated by the loss of tight junction proteins and the shedding of alveolar epithelial cells. Compared to larger TNPs (50 nm), smaller ones (8 nm) exhibit a higher accumulation in mammary glands and are more potent in causing perturbations to blood-milk barrier. An alarming finding is that the smaller TNPs (8 nm) are transferred from dams to pups through breastfeeding, likely through the disrupted blood-milk barrier. However, during the lactation period, the nutrient quality of milk from dams and the early developmental landmarks of the pups are not affected by above perturbations. PMID:25849145

  18. Time dependent changes in Schottky barrier mapping of the W/Si(001) interface utilizing ballistic electron emission microscopy

    SciTech Connect

    Durcan, Chris A.; Balsano, Robert; LaBella, Vincent P.

    2015-06-28

    The W/Si(001) Schottky barrier height is mapped to nanoscale dimensions using ballistic electron emission microscopy (BEEM) over a period of 21 days to observe changes in the interface electrostatics. Initially, the average spectrum is fit to a Schottky barrier height of 0.71 eV, and the map is uniform with 98% of the spectra able to be fit. After 21 days, the average spectrum is fit to a Schottky barrier height of 0.62 eV, and the spatial map changes dramatically with only 27% of the spectra able to be fit. Transmission electron microscopy shows the formation of an ultra-thin tungsten silicide at the interface, which increases in thickness over the 21 days. This increase is attributed to an increase in electron scattering and the changes are observed in the BEEM measurements. Interestingly, little to no change is observed in the I-V measurements throughout the 21 day period.

  19. 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

  20. 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].

  1. Temperature-Dependent Deicing Properties of Electrostatically Anchored Branched Brush Layers of Poly(ethylene oxide).

    PubMed

    Heydari, Golrokh; Tyrode, Eric; Visnevskij, Ceslav; Makuska, Ricardas; Claesson, Per M

    2016-05-01

    The hydration water of hydrophilic polymers freezes at subzero temperatures. The adsorption of such polymers will result in a hydrophilic surface layer that strongly binds water. Provided this interfacial hydration water remains liquidlike at subzero temperatures, its presence could possibly reduce ice adhesion, in particular, if the liquidlike layer is thicker than or comparable to the surface roughness. To explore this idea, a diblock copolymer, having one branched bottle-brush block of poly(ethylene oxide) and one linear cationic block, was electrostatically anchored on flat silica surfaces. The shear ice adhesion strength on such polymer-coated surfaces was investigated down to -25 °C using a homebuilt device. In addition, the temperature dependence of the ice adhesion on surfaces coated with only the cationic block, only the branched bottle-brush block, and with linear poly(ethylene oxide) was investigated. Significant ice adhesion reduction, in particular, at temperatures above -15 °C, was observed on silica surfaces coated with the electrostatically anchored diblock copolymer. Differential scanning calorimetry measurements on bulk polymer solutions demonstrate different thermal transitions of water interacting with branched and linear poly(ethylene oxide) (with hydration water melting points of about -18 and -10 °C, respectively). This difference is consistent with the low shear ice adhesion strength measured on surfaces carrying branched bottle-brush structured poly(ethylene oxide) at -10 °C, whereas no significant adhesion reduction was obtained with linear poly(ethylene oxide) at this temperature. We propose a lubrication effect of the hydration water bound to the branched bottle-brush structured poly(ethylene oxide), which, in the bulk, does not freeze until -18 °C. PMID:27064661

  2. 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

  3. A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

    SciTech Connect

    Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.; Park, Jeong Y.; Li, Yimin; Bluhm, Hendrik; Bratlie, Kaitlin M.; Zhang, Tianfu; Somorjai, Gabor A.

    2008-09-15

    CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation state at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.

  4. 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

    2015-11-01

    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. PMID:26307555

  5. 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

  6. Cdc42-Dependent Activation of NADPH Oxidase Is Involved in Ethanol-Induced Neuronal Oxidative Stress

    PubMed Central

    Wang, Xin; Ke, Zunji; Chen, Gang; Xu, Mei; Bower, Kimberly A.; Frank, Jacqueline A.; Zhang, Zhuo; Shi, Xianglin; Luo, Jia

    2012-01-01

    It has been suggested that excessive reactive oxygen species (ROS) and oxidative stress play an important role in ethanol-induced damage to both the developing and mature central nervous system (CNS). The mechanisms underlying ethanol-induced neuronal ROS, however, remain unclear. In this study, we investigated the role of NADPH oxidase (NOX) in ethanol-induced ROS generation. We demonstrated that ethanol activated NOX and inhibition of NOX reduced ethanol-promoted ROS generation. Ethanol significantly increased the expression of p47phox and p67phox, the essential subunits for NOX activation in cultured neuronal cells and the cerebral cortex of infant mice. Ethanol caused serine phosphorylation and membrane translocation of p47phox and p67phox, which were prerequisites for NOX assembly and activation. Knocking down p47phox with the small interfering RNA was sufficient to attenuate ethanol-induced ROS production and ameliorate ethanol-mediated oxidative damage, which is indicated by a decrease in protein oxidation and lipid peroxidation. Ethanol activated cell division cycle 42 (Cdc42) and overexpression of a dominant negative (DN) Cdc42 abrogate ethanol-induced NOX activation and ROS generation. These results suggest that Cdc42-dependent NOX activation mediates ethanol-induced oxidative damages to neurons. PMID:22662267

  7. Puromycin aminonucleoside increases podocyte permeability by modulating ZO-1 in an oxidative stress-dependent manner.

    PubMed

    Ha, Tae-Sun; Park, Hye-Young; Seong, Su-Bin; Ahn, Hee Yul

    2016-01-01

    Puromycin aminonucleoside (PAN)-induced nephrosis is a widely studied animal model of human idiopathic nephrotic syndrome because PAN injection into rats results in increased glomerular permeability with the characteristic ultrastructural changes in podocytes similar to human nephrosis. To investigate the role of zonula occludens (ZO)-1 and oxidative stress on PAN-induced podocyte phenotypical changes and hyperpermeability in vitro, we cultured rat and mouse podocytes and treated with various concentrations of PAN. PAN treatment increased oxidative stress level of podocytes significantly with the induction of Nox4. In addition, PAN changed the ultrastructure of podocytes, such as shortening and fusion of microvilli, and the separation of intercellular gaps, which were improved by anti-oxidative vitamin C and Nox4 siRNA. PAN also disrupted the intercellular linear ZO-1 staining and induced inner cytoplasmic re-localization of ZO-1 protein, resulting in increased podocyte intercellular permeability. PAN reduced ZO-1 protein amount and mRNA expression in a dose-dependent manner, which means that PAN could also modulate ZO-1 protein transcriptionally. However, the decreased ZO-1 protein of podocytes by PAN was improved by Nox4 siRNA transfection. Furthermore, vitamin C mitigated the quantitative and distributional disturbances of ZO-1 protein caused by PAN. Our results demonstrate that the phenotypical changes of intercellular ZO-1 by oxidative stress via Nox4 likely contribute to the glomerular hyperpermeability caused by PAN. PMID:26683996

  8. 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

  9. 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

  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. 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.

  12. 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

    2013-08-01

    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. PMID:23779084

  13. Comprehensive NO-dependent study of the products of the oxidation of atmospherically relevant aromatic compounds.

    PubMed

    Birdsall, Adam W; Elrod, Matthew J

    2011-06-01

    A comprehensive product study, performed via the turbulent flow chemical ionization mass spectrometry (TF-CIMS) technique, of the primary OH-initiated oxidation of many of the atmospherically abundant aromatic compounds was performed. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of aromatics, was detected in all cases, as were stable bicyclic species. The NO product yield dependences suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios, which are postulated to be a possible source of the inconsistencies between previous environmental chamber results and predictions from the MCM for ozone production and OH reactivity. The TF-CIMS product yield results are also compared to previous environment chamber results and to the latest MCM parametrization. PMID:21553858

  14. Molar mass and temperature dependence of the thermodiffusion of polyethylene oxide in water/ethanol mixtures

    NASA Astrophysics Data System (ADS)

    Wang, Zilin; Afanasenkau, Dzmitry; Dong, Minjie; Huang, Danni; Wiegand, Simone

    2014-08-01

    In this work, we study the molar mass dependence of the thermodiffusion of polyethylene oxide at different temperatures in ethanol, water/ethanol mixture (cwater = 0.7), and water in a molar mass range up to Mw = 180 000 g/mol. Due to the low solubility of polyethylene oxide oligomers in ethanol the measurements are limited up to Mw = 2200 g/mol. The specific water/ethanol concentration 0.7 has been chosen, because at this weight fraction the thermal diffusion coefficient, DT, of water/ethanol vanishes so that the system can be treated as a pseudo binary mixture. The addition of ethanol will degrade the solvent quality, so that we expect a change of the interaction energies between polymer and solvent. The analysis of the experimental data within a theoretical model shows the need of a refined model, which takes specific interactions into account.

  15. Alkylamine-Dependent Amino-Acid Oxidation by Lysine Monooxygenase—Fragmented Substrate of Oxygenase

    PubMed Central

    Yamamoto, Shozo; Yamauchi, Takashi; Hayaishi, Osamu

    1972-01-01

    Lysine monooxygenase catalyzes the oxygenative decarboxylation of L-lysine and produces a corresponding acid amide. L-Alanine was inactive as substrate. However, when propylamine was present, oxidation, but not oxygenation, of alanine was demonstrated with the oxygenase. Alanine was converted to pyruvate, with the liberation of ammonia and hydrogen peroxide, but propylamine remained unchanged. Other α-monoamino acids were also oxidized in the presence of alkylamines with various carbon chain lengths. The highest oxidase activity was observed when the total chain length of both amino acid and amine was nearly identical with that of lysine. Available evidence indicates that the amine-dependent amino-acid oxidase activity is associated with the lysine oxygenase activity. PMID:4509334

  16. Temperature-dependent minority carrier lifetime of crystalline silicon wafers passivated by high quality amorphous silicon oxide

    NASA Astrophysics Data System (ADS)

    Inaba, Masahiro; Todoroki, Soichiro; Nakada, Kazuyoshi; Miyajima, Shinsuke

    2016-04-01

    We investigated the effects of annealing on the temperature-dependent minority carrier lifetime of a crystalline silicon wafer passivated by hydrogenated amorphous silicon oxide. The annealing significantly affects the lifetime and its temperature dependence. Our device simulations clearly indicate that valence band offset significantly affects the temperature dependence. We also found a slight increase in the interface defect density after annealing.

  17. CoFe alloy as middle layer for strong spin dependent quantum well resonant tunneling in double barrier magnetic tunnel junctions

    SciTech Connect

    Liu, R. S.; Yang, See-Hun; Jiang, Xin; Zhang, Xiaoguang; Rice, Philip M.; Canali, Carlo M.; Parkin, S. S. P.

    2013-01-01

    We report the spin-dependent quantum well resonant tunneling effect in CoFe/MgO/CoFe/MgO/CoFeB (CoFe) double barrier magnetic tunnel junctions. The dI/dV spectra reveal clear resonant peaks for the parallel magnetization configurations, which can be matched to quantum well resonances obtained from calculation. The differential TMR exhibits an oscillatory behavior with a sign change due to the formation of the spin-dependent QW states in the middle CoFe layer. Also, we observe pronounced TMR enhancement at resonant voltages at room temperature, suggesting that it is very promising to achieve high TMR using the spin-dependent QW resonant tunneling effect.

  18. Calculation of acid-base equilibrium constants at the oxide-electrolyte interface from the dependence of oxide surface charge on pH of the electrolyte

    SciTech Connect

    Gorichev, I.G.; Dorofeev, M.V.; Batrakov, V.V.

    1994-09-01

    The dependences of the catalytic activity of oxides and acid-base properties on ph of solution are similar. A procedure is developed for calculating acid-base equilibrium constants from the dependence of the oxide surface charge q on pH. The values q can be determined by potentiometric titration of aqueous suspensions of oxides. The acid-base equilibrium constants for Fe{sub 3}O{sub 4} and CuO were calculated in accordance with the proposed procedure.

  19. 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

  20. Oxidative Stress Promotes Ligand-independent and Enhanced Ligand-dependent Tumor Necrosis Factor Receptor Signaling*

    PubMed Central

    Ozsoy, Hatice Z.; Sivasubramanian, Natarajan; Wieder, Eric D.; Pedersen, Steen; Mann, Douglas L.

    2008-01-01

    Tumor necrosis factor (TNF) receptor 1 (TNFR1, p55) and 2 (TNFR2, p75) are characterized by several cysteine-rich modules in the extracellular domain, raising the possibility that redox-induced modifications of these cysteine residues might alter TNFR function. To test this possibility, we examined fluorescence resonance energy transfer (FRET) in 293T cells transfected with CFP- and YFP-tagged TNFRs exposed to the thiol oxidant diamide. Treatment with high concentrations of diamide (1 mm) resulted in an increase in the FRET signal that was sensitive to inhibition with the reducing agent dithiothreitol, suggesting that oxidative stress resulted in TNFR self-association. Treatment of cells with low concentrations of diamide (1 μm) that was not sufficient to provoke TNFR self-association resulted in increased TNF-induced FRET signals relative to the untreated cells, suggesting that oxidative stress enhanced ligand-dependent TNFR signaling. Similar findings were obtained when the TNFR1- and TNFR2-transfected cells were pretreated with a cell-impermeable oxidase, DsbA, that catalyzes disulfide bond formation between thiol groups on cysteine residues. The changes in TNFR self-association were functionally significant, because pretreating the HeLa cells and 293T cells resulted in increased TNF-induced NF-κB activation and TNF-induced expression of IκB and syndecan-4 mRNA levels. Although pretreatment with DsbA did not result in an increase in TNF binding to TNFRs, it resulted in increased TNF-induced activation of NF-κB, consistent with an allosteric modification of the TNFRs. Taken together, these results suggest that oxidative stress promotes TNFR receptor self-interaction and ligand-independent and enhanced ligand-dependent TNF signaling. PMID:18544535

  1. 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. PMID:27535534

  2. 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

    2015-02-01

    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. PMID:25562070

  3. Cytochrome P-450 dependent ethanol oxidation. Kinetic isotope effects and absence of stereoselectivity

    SciTech Connect

    Ekstroem, G.; Norsten, C.; Cronholm, T.; Ingelman-Sundberg, M.

    1987-11-17

    Deuterium isotope effects (/sup D/(V/K)) and stereoselectivity of ethanol oxidation in cytochrome P-450 containing systems and in the xanthine-xanthine oxidase system were compared with those of yeast alcohol dehydrogenase. The isotope effects were determined by using both a noncompetitive method, including incubation of unlabeled of (1,1-/sup 2/H/sub 2/) ethanol at various concentrations, and a competitive method, where 1:1 mixtures of (1-/sup 13/C)- and (/sup 2/H/sub 6/) ethanol or (2,2,2-/sup 2/H/sub 3/)- and (1,1-/sup 2/H/sub 2/) ethanol were incubated and the acetaldehyde formed was analyzed by gas chromatography/mass spectrometry. The /sup D/(V/K) isotope effects of the cytochrome P-450 dependent ethanol oxidation were about 4 with liver microsomes from imidazole-, phenobarbital- or acetone-treated rabbits or with microsomes from acetone- or ethanol-treated rats. Similar isotope effects were reached with reconstituted membranes containing the rabbit ethanol-inducible cytochrome P-450 (LMeb), whereas control rat microsomes and membranes containing rabbit phenobarbital-inducible P-450 LM/sub 2/ oxidized the alcohol with /sup D/(V/K) of about 2.8 and 1.8, respectively. Addition of Fe/sup III/EDTA either to microsomes from phenobarbital-treated rabbits or to membranes containing P-450 LMeb significantly lowered the isotope effect. Incubations of all cytochrome P-450 containing systems of the xanthine-xanthine oxidase systems with (1R)- and (1S)-(1-/sup 2/H) ethanol, revealed, taking the isotope effects into account, that 44-66% of the ethanol oxidized had lost the 1-pro-R hydrogen. The data indicate that cytochrome P-450 dependent ethanol oxidation is not stereospecific and that cleavage of the C/sub 1/-H bond appears to be a rate-determining step in the catalysis by the ethanol-inducible form of P-450. The contribution of hydroxyl radicals in ethanol oxidation by the various enzymic systems is discussed.

  4. 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. PMID:21332218

  5. 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. PMID:25682235

  6. Focal Adhesion Kinase Controls pH-Dependent Epidermal Barrier Homeostasis by Regulating Actin-Directed Na+/H+ Exchanger 1 Plasma Membrane Localization

    PubMed Central

    Ilic, Dusko; Mao-Qiang, Man; Crumrine, Debra; Dolganov, Gregory; Larocque, Nicholas; Xu, Pu; Demerjian, Marianne; Brown, Barbara E.; Lim, Ssang-Taek; Ossovskaya, Valeria; Schlaepfer, David D.; Fisher, Susan J.; Feingold, Kenneth R.; Elias, Peter M.; Mauro, Theodora M.

    2007-01-01

    Ubiquitously expressed focal adhesion kinase (FAK), linked to multiple intracellular signaling pathways, has previously been shown to control cell motility, invasion, proliferation, and survival. Using mice with a keratinocyte-restricted deletion of fak (FAKK5 KO), we report here a novel role for FAK: maintenance of adult epidermal permeability barrier homeostasis. Abundant lacunae of unprocessed lipids in stratum corneum (SC) of FAKK5 KO mice and delayed barrier recovery pointed to malfunction of pH-dependent enzymes active in extracellular space of SC. Measuring the SC pH gradient showed significantly more neutral pH values in FAKK5 KO mice, suggesting the importance of FAK for acidification. Moreover, normal functions were restored when FAKK5 KO mice were exposed to a surface pH typical of mouse SC (pH = 5.5). Baseline levels and response to barrier disruption of secretory phospholipase A2 isoforms, enzymes that mediate generation of free fatty acids in epidermis, appeared similar in both FAKK5 KO and control littermates. We found that the critical SC acidification regulator Na+/H+ exchanger 1 failed to localize to the plasma membrane in FAK-deficient keratinocytes both in vivo and in vitro. Thus, for plasma membrane localization in terminally differentiated keratinocytes, Na+/H+ exchanger 1 requires an intact actin cytoskeleton, which is impaired in FAK-deficient cells. PMID:17525272

  7. Diesel exhaust particles induce oxidative stress, proinflammatory signaling, and P-glycoprotein up-regulation at the blood-brain barrier

    PubMed Central

    Hartz, Anika M. S.; Bauer, Björn; Block, Michelle L.; Hong, Jau-Shyong; Miller, David S.

    2008-01-01

    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 EC50 was ∼5 μg/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-α (TNF-α) 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-κB, 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.—Hartz, A. M. S., Bauer, B., Block, M. L., Hong, J.-S., Miller, D.-S. Diesel exhaust particles induce oxidative stress, proinflammatory signaling, and P-glycoprotein up-regulation at the blood-brain barrier. PMID:18474546

  8. pH-dependence of conduction type in cuprous oxide synthesized from solution

    NASA Astrophysics Data System (ADS)

    Wang, Weichao; Wu, Dangxin; Zhang, Qiming; Wang, Longcheng; Tao, Meng

    2010-06-01

    The formation of native point defects in cuprous oxide, Cu2O, synthesized from solution has been studied by first-principles calculations. Although p-type conduction is obtained in Cu2O synthesized from vacuum regardless of copper-rich or oxygen-rich conditions, intrinsically n-type Cu2O without doping can be grown in a strong acidic environment from solution. Our calculations show that both n-type and p-type Cu2O can be obtained depending on the solution pH value, which are in good agreement with our experimental results.

  9. Size-dependant heating rates of iron oxide nanoparticles for magnetic fluid hyperthermia

    PubMed Central

    Gonzales-Weimuller, Marcela; Zeisberger, Matthias; Krishnan, Kannan M.

    2015-01-01

    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. PMID:26405373

  10. Investigation about thermophysical properties of Ln{sub 2}Ce{sub 2}O{sub 7} (Ln = Sm, Er and Yb) oxides for thermal barrier coatings

    SciTech Connect

    Hongsong, Zhang; Jianguo, Lv; Gang, Li; Zheng, Zhang; Xinli, Wang

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► We successfully prepared three types of new rare earth cerium oxides. ► We measured their thermophysical properties. ► These new ceramics can be explored as candidate ceramics for thermal barrier coatings. -- Abstract: Three kinds of rare earth cerium oxides – Ln{sub 2}Ce{sub 2}O{sub 7} (Ln = Sm, Er and Yb) were prepared by solid state reaction method. Their phase compositions, microstructures and thermophysical properties were investigated. Results of X-ray diffraction reveal that pure Ln{sub 2}Ce{sub 2}O{sub 7} (Ln = Sm, Er and Yb) oxides with fluorite structure are successfully synthesized in the current research. Scanning electrical microscopy results show that their microstructures are dense and no other un-reacted oxides or inter-phases exist in the interfaces between grains. Their thermal expansion coefficients are higher than those of YSZ, while their thermal conductivities are lower than those of YSZ. The decreasing ionic radius from Sm{sup 3+} to Yb{sup 3+} results in the descending thermal expansion coefficients from Sm{sub 2}Ce{sub 2}O{sub 7} to Yb{sub 2}Ce{sub 2}O{sub 7}. The effective phonon scattering by atomic weight difference contributes to the decreasing thermal conductivities from Sm{sub 2}Ce{sub 2}O{sub 7} to Yb{sub 2}Ce{sub 2}O{sub 7}. These results imply that synthesized rare earth cerium oxides have potentials to be used as novel candidate materials for thermal barrier coatings in the future.

  11. 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).

  12. Frequency dependent negative capacitance effect and dielectric properties of swift heavy ion irradiated Ni/oxide/n-GaAs Schottky diode

    NASA Astrophysics Data System (ADS)

    Bobby, A.; Shiwakoti, N.; Verma, S.; Asokan, K.; Antony, B. K.

    2016-05-01

    The Ni/n-GaAs Schottky barrier diode having thin interfacial oxide layer was subjected to 25 MeV C4+ ion irradiation at selected fluences. The in-situ capacitance and dielectric properties were investigated in the 1 KHz to 5 MHz frequency range. The results show a decrease in capacitance with increase in ion fluence at low frequencies. Interestingly, a negative capacitance effect was also observed in this frequency range in all the samples. As a consequence, changes were observed in parameters like series resistance, conductance, dielectric loss, dielectric constant, loss tangent and ac electrical conductivity. At high frequencies, the capacitance reaches the geometric value 'C0'. The results were interpreted in terms of the generation of irradiation induced traps, carrier capture and emission from deep and shallow states and its frequency dependent saturation effects.

  13. Omentin protects against LPS-induced ARDS through suppressing pulmonary inflammation and promoting endothelial barrier via an Akt/eNOS-dependent mechanism.

    PubMed

    Qi, Di; Tang, Xumao; He, Jing; Wang, Daoxin; Zhao, Yan; Deng, Wang; Deng, Xinyu; Zhou, Guoqi; Xia, Jing; Zhong, Xi; Pu, Shenglan

    2016-01-01

    Acute respiratory distress syndrome (ARDS) is characterized by increased pulmonary inflammation and endothelial barrier permeability. Omentin has been shown to benefit obesity-related systemic vascular diseases; however, its effects on ARDS are unknown. In the present study, the level of circulating omentin in patients with ARDS was assessed to appraise its clinical significance in ARDS. Mice were subjected to systemic administration of adenoviral vector expressing omentin (Ad-omentin) and one-shot treatment of recombinant human omentin (rh-omentin) to examine omentin's effects on lipopolysaccharide (LPS)-induced ARDS. Pulmonary endothelial cells (ECs) were treated with rh-omentin to further investigate its underlying mechanism. We found that a decreased level of circulating omentin negatively correlated with white blood cells and procalcitonin in patients with ARDS. Ad-omentin protected against LPS-induced ARDS by alleviating the pulmonary inflammatory response and endothelial barrier injury in mice, accompanied by Akt/eNOS pathway activation. Treatment of pulmonary ECs with rh-omentin attenuated inflammatory response and restored adherens junctions (AJs), and cytoskeleton organization promoted endothelial barrier after LPS insult. Moreover, the omentin-mediated enhancement of EC survival and differentiation was blocked by the Akt/eNOS pathway inactivation. Therapeutic rh-omentin treatment also effectively protected against LPS-induced ARDS via the Akt/eNOS pathway. Collectively, these data indicated that omentin protects against LPS-induced ARDS by suppressing inflammation and promoting the pulmonary endothelial barrier, at least partially, through an Akt/eNOS-dependent mechanism. Therapeutic strategies aiming to restore omentin levels may be valuable for the prevention or treatment of ARDS. PMID:27607575

  14. 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.

  15. Involvement of Prx3, a Drosophila ortholog of the thiol-dependent peroxidase PRDX3, in age-dependent oxidative stress resistance.

    PubMed

    Kayashima, Yasunari; Yamakawa-Kobayashi, Kimiko

    2012-01-01

    Peroxiredoxins (Prxs) are a family of multifunctional antioxidant thioredoxin-dependent peroxidases. We used Drosophila melanogaster to examine the function of Prx3, the Drosophila homolog of human PRDX3. The oxidative stress response in adult Drosophila is age-dependent. RNAiinduced Prx3 knockdown in adult flies did not change their phenotype in normal conditions, but they had a shorter survival than the Prx3(+) controls in the presence of H2O2. The expression levels of the Prx3 were reduced by aging. These results suggest that Prx3 plays an important role in the oxidative stress response and is involved in the age-dependent competence of the oxidative stress response. PMID:23124252

  16. 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.

  17. Polarity-dependent photoemission spectra of wurtzite-type zinc oxide

    SciTech Connect

    Williams, Jesse; Yoshikawa, Hideki; Ueda, Shigenori; Yamashita, Yoshiyuki; Kobayashi, Keisuke; Adachi, Yutaka; Ohashi, Naoki; Haneda, Hajime; Ohgaki, Takeshi; Miyazaki, Hiroki; Ishigaki, Takamasa

    2012-01-30

    The polar surfaces of wurtzite-type zinc oxide (ZnO) were characterized by x-ray photoemission spectroscopy to identify the origin of the polarity dependence of the valence band spectra. A characteristic sub-peak always appeared in the valence band spectra of the (0001) face regardless of the surface preparation conditions. It also appeared in the valence band spectra of the (1012) face, but only when the photoelectron take-off angle was parallel to the c-axis of ZnO. Our analysis demonstrates that this take-off angle dependency originates not from the surface state, photoelectron diffraction, or the presence of surfactants but from the crystal polarity.

  18. Cyclic AMP-dependent phosphorylation of neuronal nitric oxide synthase mediates penile erection

    PubMed Central

    Hurt, K. Joseph; Sezen, Sena F.; Lagoda, Gwen F.; Musicki, Biljana; Rameau, Gerald A.; Snyder, Solomon H.; Burnett, Arthur L.

    2012-01-01

    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. PMID:23012472

  19. Correlation between surface chemistry and ion energy dependence of the etch yield in multicomponent oxides etching

    SciTech Connect

    Berube, P.-M.; Poirier, J.-S.; Margot, J.; Stafford, L.; Ndione, P. F.; Chaker, M.; Morandotti, R.

    2009-09-15

    The influence of surface chemistry in plasma etching of multicomponent oxides was investigated through measurements of the ion energy dependence of the etch yield. Using pulsed-laser-deposited Ca{sub x}Ba{sub (1-x)}Nb{sub 2}O{sub 6} (CBN) and SrTiO{sub 3} thin films as examples, it was found that the etching energy threshold shifts toward values larger or smaller than the sputtering threshold depending on whether or not ion-assisted chemical etching is the dominant etching pathway and whether surface chemistry is enhancing or inhibiting desorption of the film atoms. In the case of CBN films etched in an inductively coupled Cl{sub 2} plasma, it is found that the chlorine uptake is inhibiting the etching reaction, with the desorption of nonvolatile NbCl{sub 2} and BaCl{sub 2} compounds being the rate-limiting step.

  20. 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.

  1. 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. PMID:20648324

  2. Low-temperature thermal reduction of graphene oxide nanobrick walls: unique combination of high gas barrier and low resistivity in fully organic polyelectrolyte multilayer thin films.

    PubMed

    Stevens, Bart; Dessiatova, Ekaterina; Hagen, David A; Todd, Alexander D; Bielawski, Christopher W; Grunlan, Jaime C

    2014-07-01

    Layer-by-layer assembly from aqueous solutions was used to construct multilayer thin films (<200 nm) comprising polyethylenimine and graphene oxide. Low-temperature (175 °C) thermal reduction of these films improved gas barrier properties (e.g., lower permeability than SiOx), even under high humidity conditions, and enhanced their electrical conductivity to 1750 S/m. 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 packaging applications. PMID:24949524

  3. Trifluorosubstrates as mechanistic probes for an FMN-dependent l-2-hydroxy acid-oxidizing enzyme.

    PubMed

    Lederer, Florence; Vignaud, Caroline; North, Paul; Bodevin, Sabrina

    2016-09-01

    A controversy exists with respect to the mechanism of l-2-hydroxy acid oxidation by members of a family of FMN-dependent enzymes. A so-called carbanion mechanism was initially proposed, in which the active site histidine abstracts the substrate α-hydrogen as a proton, followed by electron transfer from the carbanion to the flavin. But an alternative mechanism was not incompatible with some results, a mechanism in which the active site histidine instead picks up the substrate hydroxyl proton and a hydride transfer occurs. Even though more recent experiments ruling out such a mechanism were published (Rao & Lederer (1999) Protein Science 7, 1531-1537), a few authors have subsequently interpreted their results with variant enzymes in terms of a hydride transfer. In the present work, we analyse the reactivity of trifluorolactate, a substrate analogue, with the flavocytochrome b2 (Fcb2) flavodehydrogenase domain, compared to its reactivity with an NAD-dependent lactate dehydrogenase (LDH), for which this compound is known to be an inhibitor (Pogolotti & Rupley (1973) Biochem. Biophys. Res. Commun, 55, 1214-1219). Indeed, electron attraction by the three fluorine atoms should make difficult the removal of the α-H as a hydride. We also analyse the reactivity of trifluoropyruvate with the FMN- and NAD-dependent enzymes. The results substantiate a different effect of the fluorine substituents on the two enzymes compared to their normal substrates. In the discussion we analyse the conclusions of recent papers advocating a hydride transfer mechanism for the family of l-2-hydroxy acid oxidizing FMN-dependent enzymes. PMID:27155230

  4. Composition-dependent structural and transport properties of amorphous transparent conducting oxides

    NASA Astrophysics Data System (ADS)

    Khanal, Rabi; Buchholz, D. Bruce; Chang, Robert P. H.; Medvedeva, Julia E.

    2015-05-01

    Structural properties of amorphous In-based oxides, In -X -O with X =Zn , Ga, Sn, or Ge, are investigated using ab initio molecular dynamics liquid-quench simulations. The results reveal that indium retains its average coordination of 5.0 upon 20% X fractional substitution for In, whereas X cations satisfy their natural coordination with oxygen atoms. This finding suggests that the carrier generation is primarily governed by In atoms, in accord with the observed carrier concentration in amorphous In-O and In -X -O . At the same time, the presence of X affects the number of six-coordinated In atoms as well as the oxygen sharing between the InO6 polyhedra. Based on the obtained interconnectivity and spatial distribution of the InO6 and XO x polyhedra in amorphous In -X -O , composition-dependent structural models of the amorphous oxides are derived. The results help explain our Hall mobility measurements in In -X -O thin films grown by pulsed-laser deposition and highlight the importance of long-range structural correlations in the formation of amorphous oxides and their transport properties.

  5. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles.

    PubMed

    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

  6. 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

  7. 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.

  8. Participation of P450-dependent oxidation of isoniazid in isonicotinic acid formation in rat liver.

    PubMed

    Ono, Y; Wu, X; Noda, A; Noda, H; Yoshitani, T

    1998-04-01

    By determining the formation amount of isonicotinic acid (INA) from isonicotinic acid hydrazide (isoniazid:INH) in isolated rat hepatocytes, we were able to identify the involvement of the oxidative cleavage of the acid hydrazide. INA formation from INH increased significantly using the isolated hepatocytes prepared from rats pretreated with phenobarbital (PB), 3-methylcholanthrene (3MC), dexamethazone (DEX) and rifampicin (RIF), respectively, in comparison to the control group. On the other hand, a remarkable decrease in INA formation from INH was observed by the addition of such P450 inhibitor as metyrapone or cimetidine as well as an amidase inhibitor bis(p-nitrophenyl)phosphate (BNPP) to the isolated hepatocytes prepared from PB-pretreated rats. By further experiments using rat hepatic microsomes, the oxidative pathway of INA formation in INH metabolism was determined to be P450-dependent, since NADPH and oxygen were both essential for the oxidative pathway of INH to INA and the amount of INA formation was also significantly increased by P450 inducers. Regarding acetylisoniazid (AcINH) and isonicotinic acid amide (INAA), however, INA formation by P450 was little observed in the microsomal experiments. PMID:9586587

  9. 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

  10. Microarray study of temperature-dependent sensitivity and selectivity of metal/oxide sensing interfaces

    NASA Astrophysics Data System (ADS)

    Tiffany, Jason; Cavicchi, Richard E.; Semancik, Stephen

    2001-02-01

    Conductometric gas microsensors offer the benefits of ppm-level sensitivity, real-time data, simple interfacing to electronics hardware, and low power consumption. The type of device we have been exploring consists of a sensor film deposited on a "microhotplate"- a 100 micron platform with built-in heating (to activate reactions on the sensing surface) and thermometry. We have been using combinatorial studies of 36-element arrays to characterize the relationship between sensor film composition, operating temperature, and response, as measured by the device's sensitivity and selectivity. Gases that have been tested on these arrays include methanol, ethanol, dichloromethane, propane, methane, acetone, benzene, hydrogen, and carbon monoxide, and are of interest in the management of environmental waste sites. These experiments compare tin oxide films modified by catalyst overlayers, and ultrathin metal seed layers. The seed layers are used as part of a chemical vapor deposition process that uses each array element's microheater to activate the deposition of SnO2, and control its microstructure. Low coverage (20 Ê) catalytic metals (Pd, Cu, Cr, In, Au) are deposited on the oxides by masked evaporation or sputtering. This presentation demonstrates the value of an array-based approach for developing film processing methods, measuring performance characteristics, and establishing reproducibility. It also illustrates how temperature-dependent response data for varied metal/oxide compositions can be used to tailor a microsensor array for a given application.

  11. Hodgkin and Reed-Sternberg cells of classical Hodgkin lymphoma are highly dependent on oxidative phosphorylation.

    PubMed

    Birkenmeier, Katrin; Dröse, Stefan; Wittig, Ilka; Winkelmann, Ria; Käfer, Viktoria; Döring, Claudia; Hartmann, Sylvia; Wenz, Tina; Reichert, Andreas S; Brandt, Ulrich; Hansmann, Martin-Leo

    2016-05-01

    The metabolic properties of lymphomas derived from germinal center (GC) B cells have important implications for therapeutic strategies. In this study, we have compared metabolic features of Hodgkin-Reed-Sternberg (HRS) cells, the tumor cells of classical Hodgkin's lymphoma (cHL), one of the most frequent (post-)GC-derived B-cell lymphomas, with their normal GC B cell counterparts. We found that the ratio of oxidative to nonoxidative energy conversion was clearly shifted toward oxidative phosphorylation (OXPHOS)-linked ATP synthesis in HRS cells as compared to GC B cells. Mitochondrial mass, the expression of numerous key proteins of oxidative metabolism and markers of mitochondrial biogenesis were markedly upregulated in cHL cell lines and in primary cHL cases. NFkappaB promoted this shift to OXPHOS. Functional analysis indicated that both cell growth and viability of HRS cells depended on OXPHOS. The high rates of OXPHOS correlated with an almost complete lack of lactate production in HRS cells not observed in other GC B-cell lymphoma cell lines. Overall, we conclude that OXPHOS dominates energy conversion in HRS cells, while nonoxidative ATP production plays a subordinate role. Our results suggest that OXPHOS could be a new therapeutic target and may provide an avenue toward new treatment strategies in cHL. PMID:26595876

  12. TET-mediated oxidation of methylcytosine causes TDG or NEIL glycosylase dependent gene reactivation

    PubMed Central

    Müller, Udo; Bauer, Christina; Siegl, Michael; Rottach, Andrea; Leonhardt, Heinrich

    2014-01-01

    The discovery of hydroxymethyl-, formyl- and carboxylcytosine, generated through oxidation of methylcytosine by TET dioxygenases, raised the question how these modifications contribute to epigenetic regulation. As they are subjected to complex regulation in vivo, we dissected links to gene expression with in vitro modified reporter constructs. We used an Oct4 promoter-driven reporter gene and demonstrated that in vitro methylation causes gene silencing while subsequent oxidation with purified catalytic domain of TET1 leads to gene reactivation. To identify proteins involved in this pathway we screened for TET interacting factors and identified TDG, PARP1, XRCC1 and LIG3 that are involved in base-excision repair. Knockout and rescue experiments demonstrated that gene reactivation depended on the glycosylase TDG, but not MBD4, while NEIL1, 2 and 3 could partially rescue the loss of TDG. These results clearly show that oxidation of methylcytosine by TET dioxygenases and subsequent removal by TDG or NEIL glycosylases and the BER pathway results in reactivation of epigenetically silenced genes. PMID:24948610

  13. Effects of aminosalicylates and immunosuppressive agents on nitric oxide-dependent N-nitrosation reactions.

    PubMed

    Grisham, M B; Miles, A M

    1994-05-18

    Recent studies have demonstrated that nitric oxide (NO) rapidly and spontaneously decomposes in oxygenated solutions to generate potent N-nitrosating agents. These electrophilic substances have been shown to mediate mutagenesis and carcinogenesis via the formation of aliphatic and aromatic nitrosamines. We have also demonstrated that extravasated neutrophils and macrophages produce significant amounts of N-nitrosating agents derived exclusively from NO. During the course of these studies, we found that certain antioxidants, including 5-aminosalicylic acid (5-ASA), inhibited the leukocyte-mediated N-nitrosation reaction. Because 5-ASA and other anti-inflammatory and immunosuppressive drugs are used to treat inflammatory bowel disease, we wondered if any of these other compounds might also modulate N-nitrosation reactions in vitro. Therefore, the objectives of this study were to assess the ability of aminosalicylates and certain immunosuppressive agents to inhibit NO-dependent N-nitrosation of a model aromatic amine (2,3-diaminonaphthalene) and to determine whether this inhibitory activity correlated with their oxidation potential. We found that the concentrations necessary to inhibit the N-nitrosation reaction by 50% (IC50) were 25, 50 and 100 microM for 5-ASA, olsalazine (dimeric 5-ASA) and sulfasalazine, respectively. In contrast, sulfapyridine, 4-ASA, N-acetyl-5-ASA, 6-mercaptopurine, azathioprine, and methotrexate were either much less effective or inactive at inhibiting the N-nitrosation reaction. Although 5-ASA was able to fully scavenge the stable free radical 1,1-diphenyl-2-picrylhydrazyl, neither olsalazine nor sulfasalazine was found to be effective at scavenging this weak oxidant. We did find that olsalazine possessed an oxidation potential substantially less than that of sulfasalazine, suggesting that it may, in fact, scavenge more potent oxidizing agents such as the N-nitrosating agent. We conclude that 5-ASA and olsalazine inhibit NO-dependent N

  14. t-PA, but not desmoteplase, induces plasmin-dependent opening of a blood-brain barrier model under normoxic and ischaemic conditions.

    PubMed

    Freeman, Roxann; Niego, Be'eri; Croucher, David R; Pedersen, Lars O; Medcalf, Robert L

    2014-05-27

    Tissue-type plasminogen activator (t-PA) is the only thrombolytic treatment available for patients with acute ischaemic stroke. However, t-PA can increase permeability of the blood-brain barrier (BBB). Desmoteplase is a plasminogen activator derived from the common vampire bat, currently under clinical development for ischaemic stroke. We compared how t-PA and desmoteplase influenced BBB permeability using a human in vitro model where primary brain endothelial cells (BEC) and astrocytes are co-cultured on the opposite sides of a porous membrane. Permeability changes were evaluated 6 or 24h post-stimulation by passage of fluorescent albumin across the membrane. Under normoxic conditions, t-PA, but not desmoteplase, increased BBB permeability. Surprisingly, the ability of t-PA to affect the barrier was lost under conditions of oxygen-glucose deprivation (OGD). Addition of plasminogen re-sensitised the BBB to the action of t-PA under both normoxia and OGD, but did not affect the inert behaviour of desmoteplase, even when digested fibrinogen was added to ensure optimal plasmin generation. These observations coincided with plasmin-dependent changes in astrocyte and BEC morphology and disruption of tight junction proteins in BECs, specifically initiated by t-PA but not by desmoteplase. Finally, inhibition of plasmin post-stimulation with t-PA and plasminogen, especially within 2h, protected the BBB against t-PA-mediated barrier opening. Hence t-PA, but not desmoteplase, increases BBB permeability under both normoxic and OGD conditions in a reversible, plasmin-dependent process. The inability of desmoteplase to increase permeability despite its capacity to generate plasmin provides further support for its use as thrombolytic in patients with ischaemic stroke. PMID:24675027

  15. 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. PMID:25697357

  16. Regulatory mechanism of the flavoprotein Tah18-dependent nitric oxide synthesis and cell death in yeast.

    PubMed

    Yoshikawa, Yuki; Nasuno, Ryo; Kawahara, Nobuhiro; Nishimura, Akira; Watanabe, Daisuke; Takagi, Hiroshi

    2016-07-01

    Nitric oxide (NO) is a ubiquitous signaling molecule involved in the regulation of a large number of cellular functions. The regulatory mechanism of NO generation in unicellular eukaryotic yeast cells is poorly understood due to the lack of mammalian and bacterial NO synthase (NOS) orthologues, even though yeast produces NO under oxidative stress conditions. Recently, we reported that the flavoprotein Tah18, which was previously shown to transfer electrons to the iron-sulfur cluster protein Dre2, is involved in NOS-like activity in the yeast Saccharomyces cerevisiae. On the other hand, Tah18 was reported to promote apoptotic cell death after exposure to hydrogen peroxide (H2O2). Here, we showed that NOS-like activity requiring Tah18 induced cell death upon treatment with H2O2. Our experimental results also indicate that Tah18-dependent NO production and cell death are suppressed by enhancement of the interaction between Tah18 and its molecular partner Dre2. Our findings indicate that the Tah18-Dre2 complex regulates cell death as a molecular switch via Tah18-dependent NOS-like activity in response to environmental changes. PMID:27178802

  17. 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.

  18. CO Oxidation on Au/TiO2: Condition-Dependent Active Sites and Mechanistic Pathways.

    PubMed

    Wang, Yang-Gang; Cantu, David C; Lee, Mal-Soon; Li, Jun; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

    2016-08-24

    We present results of ab initio electronic structure and molecular dynamics simulations (AIMD), as well as a microkinetic model of CO oxidation catalyzed by TiO2 supported Au nanocatalysts. A coverage-dependent microkinetic analysis, based on energetics obtained with density functional methods, shows that the dominant kinetic pathway, activated oxygen species, and catalytic active sites are all strongly depended on both temperature and oxygen partial pressure. Under oxidizing conditions and T < 400 K, the prevalent pathway involves a dynamic single atom catalytic mechanism. This reaction is catalyzed by a transient Au-CO species that migrates from the Au-cluster onto a surface oxygen adatom. It subsequently reacts with the TiO2 support via a Mars van Krevelen mechanism to form CO2 and finally the Au atom reintegrates back into the gold cluster to complete the catalytic cycle. At 300 ≤ T ≤ 600 K, oxygen-bound single Oad-Au(+)-CO sites and the perimeter Au-sites of the nanoparticle work in tandem to optimally catalyze the reaction. Above 600 K, a variety of alternate pathways associated with both single-atom and the perimeter sites of the Au nanoparticle are found to be active. Under low oxygen pressures, Oad-Au(+)-CO species can be a source of catalyst deactivation and the dominant pathway involves only Au-perimeter sites. A detailed comparison of the current model and the existing literature resolves many apparent inconsistencies in the mechanistic interpretations. PMID:27480512

  19. 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

  20. 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

  1. 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. PMID:25257342

  2. A planar Al-Si Schottky barrier metal-oxide-semiconductor field effect transistor operated at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Purches, W. E.; Rossi, A.; Zhao, R.; Kafanov, S.; Duty, T. L.; Dzurak, A. S.; Rogge, S.; Tettamanzi, G. C.

    2015-08-01

    Schottky Barrier-MOSFET technology offers intriguing possibilities for cryogenic nano-scale devices, such as Si quantum devices and superconducting devices. We present experimental results on a device architecture where the gate electrode is self-aligned with the device channel and overlaps the source and drain electrodes. This facilitates a sub-5 nm gap between the source/drain and channel, and no spacers are required. At cryogenic temperatures, such devices function as p-MOS Tunnel FETs, as determined by the Schottky barrier at the Al-Si interface, and as a further advantage, fabrication processes are compatible with both CMOS and superconducting logic technology.

  3. pH Dependent Mechanism of Nitric Oxide Release in Nitrophorins 2 and 4

    PubMed Central

    Swails, Jason M.; Meng, Yilin; Walker, F. Ann; Marti, Marcelo A.; Estrin, Dario A.; Roitberg, Adrian E.

    2009-01-01

    Nitrophorins are NO carrier proteins that transport and release NO through a pH dependent conformational change. They bind NO tightly in a low pH environment and release it in a higher pH environment. Experimental evidence shows that the increase in the NO dissociation equilibrium constant, Kd, is due mainly to an increase in the NO release rate. Structural and kinetic data strongly suggest that NPs control NO escape by modulating its migration from the active site to the solvent through a pH dependent conformational change. NP2 and NP4 are two representative proteins of the family displaying a 39% overall sequence identity and, interestingly, NP2 releases NO slower than NP4. The proposal that NPs' NO release relies mainly on the NO escape rate make NPs a very peculiar case among typical heme proteins. The connection between the pH dependent conformational change and ligand release mechanism is not fully understood and the structural basis for the pH induced structural transition and the different NO release patterns in NPs are unresolved, yet interesting issues. In this work we have used state of the art molecular dynamics simulations to study the NO escape process in NP2 and NP4 in both the low and high pH states. Our results show that both NPs modulate NO release by switching between a “closed” conformation in a low pH environment and an “open” conformation at higher pH. In both proteins the change is caused by the differential protonation of a common residue Asp30 in NP4 and Asp29 in NP2, and the NO escape route is conserved. Finally, our results show that in NP2, the conformational change to the “open” conformation is smaller than that for NP4 which results in a higher barrier for NO release. PMID:19159340

  4. Rat liver microsomal cytochrome P450-dependent oxidation of 3,5-disubstituted analogues of paracetamol.

    PubMed

    Bessems, J G; Te Koppele, J M; Van Dijk, P A; Van Stee, L L; Commandeur, J N; Vermeulen, N P

    1996-06-01

    1. The cytochrome P450-dependent binding of paracetamol and a series of 3,5-disubstituted paracetamol analogues (R = -F, -Cl, -Br, -I, -CH3, -C2H5, -iC3H7) have been determined with beta-naphthoflavone (beta NF)-induced rat liver microsomes and produced reverse type I spectral changes. Ks,app varied from 0.14 mM for 3,5-diiC3H7-paracetamol to 2.8 mM for paracetamol. 2. All seven analogues underwent rat liver microsomal cytochrome P450-dependent oxidation, as reflected by the formation of GSSG in the presence of GSH. The GSSG-formation was increased in all cases upon pretreatment of rats by beta-naphthoflavone (beta NF) and was generally decreased upon pretreatment by phenobarbital (PB). 3. Rat liver microsomal cytochrome P450 as well as horseradish peroxidase catalysed the formation of 3,5-disubstituted NAPQI analogues from the corresponding parent compounds, as identified by UV-spectrophotometry of the NAPQI analogues and by GC/MS detection of the following GSH-conjugates: 2-glutathione-S-yl-3,5-dimethyl-1,4-dihydroxybenzene, 2-glutathione-S-yl-3,5-dichloro-paracetamol, and 2-glutathione-S-yl-3,5-dibromo-paracetamol. 4. In liver microsomal (beta NF-induced) incubations, apparent K(m) values, as determined for the cytochrome P450 catalysis-dependent oxidation of GSH, for seven 3,5-disubstituted paracetamol analogues (R = -F, -Cl, -Br, -I, -CH3, -C2H5, iC3H7) varied from 0.07 to 0.64 mM. Paracetamol exhibited an apparent K(m) of 0.73 mM. Apparent Vmax values for the cytochrome P450 catalysis dependent oxidation of GSH varied from 0.66 nmol min-1 mg-1 protein for paracetamol to 3.0 nmol min-1 mg-1 protein for 3,5-dimethyl-paracetamol. PMID:8810035

  5. Study of temperature-dependent ultrathin oxide growth on Si(111) using variable-angle spectroscopic ellipsometry

    NASA Technical Reports Server (NTRS)

    De, Bhola N.; Woollam, John A.

    1990-01-01

    The monolayer-sensitive variable-angle spectroscopic ellipsometry technique was used to study the temperature-dependent growth mechanisms of an ultrathin oxide layer on top of silicon. The oxidation was done in atomic oxygen produced in a pure oxygen plasma and driven by an RF power source. The results have been compared with the recently proposed model of Murali and Murarka for ultrathin oxide growth on top of silicon. The activation energies of different growth parameters associated with the oxide growth have also been determined.

  6. Damage-free back channel wet-etch process in amorphous indium-zinc-oxide thin-film transistors using a carbon-nanofilm barrier layer.

    PubMed

    Luo, Dongxiang; Zhao, Mingjie; Xu, Miao; Li, Min; Chen, Zikai; Wang, Lang; Zou, Jianhua; Tao, Hong; Wang, Lei; Peng, Junbiao

    2014-07-23

    Amorphous indium-zinc-oxide thin film transistors (IZO-TFTs) with damage-free back channel wet-etch (BCE) process were investigated. A carbon (C) nanofilm was inserted into the interface between IZO layer and source/drain (S/D) electrodes as a barrier layer. Transmittance electron microscope images revealed that the 3 nm-thick C nanofilm exhibited a good corrosion resistance to a commonly used H3PO4-based etchant and could be easily eliminated. The TFT device with a 3 nm-thick C barrier layer showed a saturated field effect mobility of 14.4 cm(2) V(-1) s(-1), a subthreshold swing of 0.21 V/decade, an on-to-off current ratio of 8.3 × 10(10), and a threshold voltage of 2.0 V. The favorable electrical performance of this kind of IZO-TFTs was due to the protection of the inserted C to IZO layer in the back-channel-etch process. Moreover, the low contact resistance of the devices was proved to be due to the graphitization of the C nanofilms after annealing. In addition, the hysteresis and thermal stress testing confirmed that the usage of C barrier nanofilms is an effective method to fabricate the damage-free BCE-type devices with high reliability. PMID:24969359

  7. Zinc oxide influences mitogen-activated protein kinase and TGF-β1 signaling pathways, and enhances intestinal barrier integrity in weaned pigs.

    PubMed

    Song, Ze He; Xiao, Kan; Ke, Ya Lu; Jiao, Le Fei; Hu, Cai Hong

    2015-05-01

    Weaning is the most significant event in the life of pigs and is always related with intestinal disruption. Although it is well known that zinc oxide (ZnO) exerts beneficial effects on the intestinal barrier, the mechanisms underlying these effects have not yet been fully elucidated. We examined whether ZnO protects the intestinal barrier via mitogen-activated protein kinases and TGF-β1 signaling pathways. Twelve barrows weaned at 21 d of age were randomly assigned to two treatments (0 verus 2200 mg Zn/kg from ZnO) for 1 wk. The results showed that supplementation with ZnO increased daily gain and feed intake, and decreased postweaning scour scores. ZnO improved intestinal morphology, as indicated by increased villus height and villus height:crypt depth ratio, and intestinal barrier function, indicated by increased transepithelial electrical resistance and decreased mucosal-to-serosal permeability to 4-ku FITC dextran. ZnO decreased the ratios of the phosphorylated to total JNK and p38 (p-JNK/JNK and p-p38/p38), while it increased the ratio of ERK (p-ERK/ERK). Supplementation with ZnO increased intestinal TGF-β1 expression. The results indicate that supplementation with ZnO activates ERK ½, and inhibits JNK and p38 signaling pathways, and increases intestinal TGF-β1 expression in weaned pigs. PMID:24917655

  8. 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.

  9. 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%.

  10. Pif1 removes a Rap1-dependent barrier to the strand displacement activity of DNA polymerase δ

    PubMed Central

    Koc, Katrina N.; Singh, Saurabh P.; Stodola, Joseph L.; Burgers, Peter M.; Galletto, Roberto

    2016-01-01

    Using an in vitro reconstituted system in this work we provide direct evidence that the yeast repressor/activator protein 1 (Rap1), tightly bound to its consensus site, forms a strong non-polar barrier for the strand displacement activity of DNA polymerase δ. We propose that relief of inhibition may be mediated by the activity of an accessory helicase. To this end, we show that Pif1, a 5′–3′ helicase, not only stimulates the strand displacement activity of Pol δ but it also allows efficient replication through the block, by removing bound Rap1 in front of the polymerase. This stimulatory activity of Pif1 is not limited to the displacement of a single Rap1 molecule; Pif1 also allows Pol δ to carry out DNA synthesis across an array of bound Rap1 molecules that mimics a telomeric DNA-protein assembly. This activity of Pif1 represents a novel function of this helicase during DNA replication. PMID:27001517

  11. NITRIC OXIDE-DEPENDENT PROTEASOMAL DEGRADATION OF CYTOCHROME P450 2B PROTEINS*

    PubMed Central

    Lee, Choon-Myung; Kim, Bong-Yoon; Li, Lian; Morgan, Edward T.

    2007-01-01

    Exposure to inflammatory agents or cytokines causes the suppression of cytochrome P450 (CYP) enzyme activities and expression in liver and primary hepatocyte cultures. We showed previously that phenobarbital-induced CYP2B protein is down-regulated in primary cultures of rat hepatocytes following exposure to bacterial endotoxin (LPS) in a nitric oxide (NO)-dependent manner. In the present study, we found that CYP2B proteins in primary rat hepatocyte cultures were suppressed more than 60% after 6h treatment with interleukin-1β (IL-1). This effect was NO-dependent, and treatment of cells with the NO-donors (Z)-1-[2-(2-aminoethyl)-N-(2-ammonioethyl)amino] diazen-1-ium-1,2-diolate (NOC-18), S-nitrosoglutathione (GSNO), and S-nitroso, N-acetylpenicillamine (SNAP) also suppressed CYP2B proteins. However, the down-regulation by IL-1 was insensitive to inhibition of cGMP-dependent protein kinases. The down-regulation by IL-1 or NO donors was abolished by treatments with the proteasome inhibitors MG132 and lactacystin that did not affect NO production. The calpain inhibitor E64-d or the lysosomal protease inhibitors NH4Cl and chloroquine did not attenuate the down-regulation of CYP2B by IL-1. Treatment of HeLa cells expressing c-myc-tagged CYP2B1 with NOC-18 down-regulated its expression and enhanced its ubiquitination. Treatment of rat liver microsomes with GSNO caused S-nitrosylation of CYP2B protein, and enhanced the ubiquitination pattern of CYP2B compared to unmodified CYP2B in an in vitro ubiquitination assay. These data are consistent with the hypothesis that NO-dependent CYP2B ubiquitination and proteasomal degradation are dependent on protein modification by reactive nitrogen species. PMID:17993647

  12. Postischemic vasodilation in human forearm is dependent on endothelium-derived nitric oxide.

    PubMed

    Meredith, I T; Currie, K E; Anderson, T J; Roddy, M A; Ganz, P; Creager, M A

    1996-04-01

    Although endothelium-derived nitric oxide contributes to basal vascular tone, little is known about its role in regulating blood flow during changes in metabolic supply and demand. We examined the contribution of endothelium-derived nitric oxide to reactive hyperemia in the forearm of 20 normal subjects (12 women, 8 men) aged 27 +/- 4 yr (means +/- SD), using the nitric oxide synthase inhibitor, NG-monomethyl-L-arginine (L-NMMA). Forearm ischemia was induced by suprasystolic blood pressure cuff inflation for 5 min, and the subsequent hyperemic flow was recorded for 5 min using venous occlusion strain-gauge plethysmography. The efficacy of nitric oxide blockade was tested by comparing the dose-response relationship to the endothelium-dependent agonist, acetylcholine (3, 10, and 30 mg/min), before and after intra-arterial infusion of up to 2,000 mg/min of L-NMMA. L-NMMA produced a significant downward and rightward shift in the dose-response relationship to acetylcholine and a 39% reduction in response to the maximum dose (P < 0.001). In the presence of L-NMMA, peak hyperemic flow was reduced 16% (26.5 +/- 2.1 to 22.3 +/- 1.5 ml.min-1.100 ml of forearm-1, P < 0.03), and the minimum forearm vascular resistance was increased 22.8% (3.5 +/- 0.3 to 4.3 +/- 0.4 mmHg.ml-1.min.100 ml, P < 0.02). Total hyperemia, calculated from the area under the flow vs. time curve, at 1 and 5 min after cuff release was 17 and 23% less, respectively (13.6 +/- 1.2 vs. 11.3 +/- 1.1 and 31.8 +/- 2.7 vs. 24.6 +/- 1.8 ml/100 ml, P < 0.002), following L-NMMA. These data suggest that endothelium-derived nitric oxide plays a role in both reactive hyperemia and in the maintenance of the hyperemic response following ischemia in the forearm. PMID:8967386

  13. Folic acid supplementation improves microvascular function in older adults through nitric oxide-dependent mechanisms.

    PubMed

    Stanhewicz, Anna E; Alexander, Lacy M; Kenney, W Larry

    2015-07-01

    Older adults have reduced vascular endothelial function, evidenced by attenuated nitric oxide (NO)-dependent cutaneous vasodilatation. Folic acid and its metabolite, 5-methyltetrahydrofolate (5-MTHF), are reported to improve vessel function. We hypothesized that (i) local 5-MTHF administration and (ii) chronic folic acid supplementation would improve cutaneous microvascular function in ageing through NO-dependent mechanisms. There were two separate studies in which there were 11 young (Y: 22 ± 1 years) and 11 older (O: 71 ± 3 years) participants. In both studies, two intradermal microdialysis fibres were placed in the forearm skin for local delivery of lactated Ringer's solution with or without 5 mM 5-MTHF. Red cell flux was measured by laser-Doppler flowmetry. Cutaneous vascular conductance [CVC=red cell flux/mean arterial pressure] was normalized as percentage maximum CVC (%CVCmax) (28 mM sodium nitroprusside, local temperature 43°C). In study 1 after CVC plateaued during local heating, 20 mM NG-nitro-L-arginine methyl ester (L-NAME) was perfused at each site to quantify NO-dependent vasodilatation. The local heating plateau (%CVCmax: O = 82 ± 3 vs Y = 96 ± 1, P = 0.002) and NO-dependent vasodilatation (%CVCmax: O = 26 ± 6% vs Y = 49 ± 5, P = 0.03) were attenuated in older participants. 5-MTHF augmented the overall (%CVCmax = 91 ± 2, P = 0.03) and NO-dependent (%CVCmax = 43 ± 9%, P = 0.04) vasodilatation in older but not young participants. In study 2 the participants ingested folic acid (5 mg/day) or placebo for 6 weeks in a randomized, double-blind, crossover design. A rise in oral temperature of 1°C was induced using a water-perfused suit, body temperature was held and 20 mM L-NAME was perfused at each site. Older participants had attenuated reflex (%CVCmax: O = 31 ± 8 vs Y = 44 ± 5, P = 0.001) and NO-dependent (%CVCmax: O = 9 ± 2 vs Y = 21 ± 2, P = 0.003) vasodilatation. Folic acid increased CVC (%CVCmax = 47 ± 5%, P = 0.001) and NO-dependent

  14. Reduction of Cu(II) by lipid hydroperoxides: implications for the copper-dependent oxidation of low-density lipoprotein.

    PubMed Central

    Patel, R P; Svistunenko, D; Wilson, M T; Darley-Usmar, V M

    1997-01-01

    The Cu(II)-promoted oxidation of lipids is a lipid hydroperoxide (LOOH)-dependent process that has been used routinely to assess the oxidizability of low-density lipoprotein (LDL) in human subjects. Metal-dependent redox reactions, including those mediated by copper, have been implicated in the pathogenesis ofatherosclerosis. Despite its widespread use and possible biological significance, key elements of the mechanism are not clear. For example, although it is evident that copper acts as a catalyst, which implies a redox cycle between the Cu(II) and Cu(I) redox states, the reductants remain uncertain. In LDL these could include alpha-tocopherol, amino acid residues on the protein and LOOH. However, both alpha-tocopherol and amino acid residues are probably consumed before the most rapid phase of lipid peroxidation occurs, suggesting that another reductant must be donating electrons to Cu(II), the most likely candidate being LOOH. This role has been disputed, since LDLs nominally devoid of LOOH are still capable of reducing Cu(II) to Cu(I) and thermodynamic calculations for this reaction are not favourable. Direct investigation of the role of LOOH as reductant has not been reported and in the present study, using simple lipid systems and LDL, we have re-examined this issue using the Cu(I) chelator bathocuproine. We have shown that Cu(II) may promote lipid peroxidation in liposomes, which do not contain either protein or alpha-tocopherol, and that this is associated with reduction to Cu(I). The data also indicate that an equilibrium between free Cu(II) and LOOH exists, which only in the presence of an oxidizable substrate, i.e. unsaturated fatty acids, is shifted towards formation of Cu(I) and lipid-derived peroxyl radicals. We propose that reduction of Cu(II) by LOOH is a necessary component in sustaining the propagation of lipid peroxidation and that the formation of peroxyl radicals and their products in a lipid environment is sufficient to overcome thermodynamic

  15. Cardioprotection by H2S Donors: Nitric Oxide-Dependent and ‑Independent Mechanisms.

    PubMed

    Chatzianastasiou, Athanasia; Bibli, Sofia-Iris; Andreadou, Ioanna; Efentakis, Panagiotis; Kaludercic, Nina; Wood, Mark E; Whiteman, Matthew; Di Lisa, Fabio; Daiber, Andreas; Manolopoulos, Vangelis G; Szabó, Csaba; Papapetropoulos, Andreas

    2016-09-01

    Hydrogen sulfide (H2S) is a signaling molecule with protective effects in the cardiovascular system. To harness the therapeutic potential of H2S, a number of donors have been developed. The present study compares the cardioprotective actions of representative H2S donors from different classes and studies their mechanisms of action in myocardial injury in vitro and in vivo. Exposure of cardiomyocytes to H2O2 led to significant cytotoxicity, which was inhibited by sodium sulfide (Na2S), thiovaline (TV), GYY4137 [morpholin-4-ium 4 methoxyphenyl(morpholino) phosphinodithioate], and AP39 [(10-oxo-10-(4-(3-thioxo-3H-1,2-dithiol5yl)phenoxy)decyl) triphenylphospho-nium bromide]. Inhibition of nitric oxide (NO) synthesis prevented the cytoprotective effects of Na2S and TV, but not GYY4137 and AP39, against H2O2-induced cardiomyocyte injury. Mice subjected to left anterior descending coronary ligation were protected from ischemia-reperfusion injury by the H2S donors tested. Inhibition of nitric oxide synthase (NOS) in vivo blocked only the beneficial effect of Na2S. Moreover, Na2S, but not AP39, administration enhanced the phosphorylation of endothelial NOS and vasodilator-associated phosphoprotein. Both Na2S and AP39 reduced infarct size in mice lacking cyclophilin-D (CypD), a modulator of the mitochondrial permeability transition pore (PTP). Nevertheless, only AP39 displayed a direct effect on mitochondria by increasing the mitochondrial Ca(2+) retention capacity, which is evidence of decreased propensity to undergo permeability transition. We conclude that although all the H2S donors we tested limited infarct size, the pathways involved were not conserved. Na2S had no direct effects on PTP opening, and its action was nitric oxide dependent. In contrast, the cardioprotection exhibited by AP39 could result from a direct inhibitory effect on PTP acting at a site different than CypD. PMID:27342567

  16. 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

  17. CD36 Binds Oxidized Low Density Lipoprotein (LDL) in a Mechanism Dependent upon Fatty Acid Binding*

    PubMed Central

    Jay, Anthony G.; Chen, Alexander N.; Paz, Miguel A.; Hung, Justin P.; Hamilton, James A.

    2015-01-01

    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. PMID:25555908

  18. Metformin decreases glucose oxidation and increases the dependency of prostate cancer cells on reductive glutamine metabolism

    PubMed Central

    Fendt, Sarah-Maria; Bell, Eric L.; Keibler, Mark A.; Davidson, Shawn M.; Wirth, Gregory J.; Fiske, Brian; Mayers, Jared R.; Schwab, Matthias; Bellinger, Gary; Csibi, Alfredo; Patnaik, Akash; Jose Blouin, Marie; Cantley, Lewis C.; Guarente, Leonard; Blenis, John; Pollak, Michael N.; Olumi, Aria F.

    2013-01-01

    Metformin inhibits cancer cell proliferation and epidemiology studies suggest an association with increased survival in cancer patients taking metformin, however, the mechanism by which metformin improves cancer outcomes remains controversial. To explore how metformin might directly affect cancer cells, we analyzed how metformin altered the metabolism of prostate cancer cells and tumors. We found that metformin decreased glucose oxidation and increased dependency on reductive glutamine metabolism in both cancer cell lines and in a mouse model of prostate cancer. Inhibition of glutamine anaplerosis in the presence of metformin further attenuated proliferation while increasing glutamine metabolism rescued the proliferative defect induced by metformin. These data suggest that interfering with glutamine may synergize with metformin to improve outcomes in patients with prostate cancer. PMID:23687346

  19. Three-dimensional and time-dependent simulation of a planar solid oxide fuel cell stack

    NASA Astrophysics Data System (ADS)

    Achenbach, E.

    1994-04-01

    The mathematical simulation of a planar solid oxide fuel cell (SOFC) is presented. The model accounts for three-dimensional and time-dependent effects. Internal methane-steam reforming and recycling of the anode gas are also considered. The effects of different flow manifolding, i.e., cross-, co-, or counter-flow are discussed. After a short description of the mathematical procedure, computational results are presented. In particular the distribution of the gases, of the current density and of the solid structure temperature across the cell are shown. Furthermore the effects of different flow manifolding, of radiation from the outer stack surface to the surroundings and of anode gas recycling on the operating conditions of the stack are considered. The response of the cell voltage to a load change is also discussed.

  20. 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

  1. Copper control of bacterial nitrous oxide emission and its impact on vitamin B12-dependent metabolism

    PubMed Central

    Sullivan, Matthew J.; Gates, Andrew J.; Appia-Ayme, Corinne; Rowley, Gary; Richardson, David J.

    2013-01-01

    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. PMID:24248380

  2. Temperature dependence of resistive switching behaviors in resistive random access memory based on graphene oxide film

    NASA Astrophysics Data System (ADS)

    Yi, Mingdong; Cao, Yong; Ling, Haifeng; Du, Zhuzhu; Wang, Laiyuan; Yang, Tao; Fan, Quli; Xie, Linghai; Huang, Wei

    2014-05-01

    We reported resistive switching behaviors in the resistive random access memory (RRAM) devices based on the different annealing temperatures of graphene oxide (GO) film as active layers. It was found that the resistive switching characteristics of an indium tin oxide (ITO)/GO/Ag structure have a strong dependence on the annealing temperature of GO film. When the annealing temperature of the GO film was 20 °C, the devices showed typical write-once-read-many-times (WORM) type memory behaviors, which have good memory performance with a higher ON/OFF current ratio (˜104), the higher the high resistance state (HRS)/low resistance state (LRS) ratio (˜105) and stable retention characteristics (>103 s) under lower programming voltage (-1 V and -0.5 V). With the increasing annealing temperature of GO film, the resistive switching behavior of RRAM devices gradually weakened and eventually disappeared. This phenomenon could be understood by the different energy level distributions of the charge traps in GO film, and the different charge injection ability from the Ag electrode to GO film, which is caused by the different annealing temperatures of the GO film.

  3. Cultivation of nitrite-dependent anaerobic methane-oxidizing bacteria: impact of reactor configuration.

    PubMed

    Hu, Baolan; He, Zhanfei; Geng, Sha; Cai, Chen; Lou, Liping; Zheng, Ping; Xu, Xinhua

    2014-09-01

    Nitrite-dependent anaerobic methane oxidation (n-damo) is mediated by bacteria that anaerobically oxidize methane coupled with nitrite reduction and is a potential bioprocess for wastewater treatment. In this work, the effect of reactor configuration on n-damo bacterial cultivation was investigated. A magnetically stirred gas lift reactor (MSGLR), a sequencing batch reactor (SBR), and a continuously stirred tank reactor (CSTR) were selected to cultivate the bacteria. Microbial community was monitored by using quantitative PCR, 16S rRNA gene sequencing, pmoA gene sequencing, and fluorescence in situ hybridization (FISH). The effects of substrate inhibition, methane mass transfer, and biomass washout in the three reactors were focused on. The results indicated that the MSGLR had the best performance among the three reactor systems, with the highest total and specific n-damo activities. Its maximum volumetric nitrogen removal rate was up to 76.9 mg N L(-1) day(-1), which was higher than previously reported values (5.1-37.8 mg N L(-1) d(-1)). PMID:24880628

  4. IMMUNE TOLERANCE INDUCTION BY APOPTOTIC CELLS REQUIRES CASPASE-DEPENDENT OXIDATION OF HMGB1

    PubMed Central

    Kazama, Hirotaka; Ricci, Jean-Ehrland; Herndon, John M.; Hoppe, George; Green, Douglas R.; Ferguson, Thomas A.

    2009-01-01

    SUMMARY The mammalian immune system discriminates between modes of cell death, with necrosis often resulting in inflammation and adaptive immunity, while apoptosis tends to be anti-inflammatory, promoting immune tolerance. In many systems immune tolerance can be established through cross presentation of antigens derived from apoptotic cells via the MHC class I pathway to CD8+ T cells. We have examined the features of apoptosis responsible for tolerance to cell-mediated immune responses in vivo, specifically the roles of caspases and the mitochondria. Our results show that caspase activation targets the mitochondria to produce ROS, which are critical to tolerance induction by apoptotic cells. ROS oxidizes the potential danger signal HMGB1 released from dying cells, thereby neutralizing its stimulatory activity and promoting tolerance. Apoptotic cells failed to induce tolerance and instead stimulated immune responses when caspase-dependent ROS activity was prohibited by scavenging or by mutation of a mitochondrial caspase target, p75 NDUSF1. Similarly blocking sites of oxidation in HMGB1 prevented tolerance induction by apoptotic cells. These results suggest that caspase orchestrated mitochondrial events determine the impact of apoptotic cells on the immune response. PMID:18631454

  5. Electrode dependent interfacial layer variation in metal-oxide-semiconductor capacitor

    NASA Astrophysics Data System (ADS)

    Park, I.-S.; Jung, Y. C.; Lee, M.; Seong, S.; Ahn, J.

    2014-03-01

    The interfacial layer between oxide and semiconductor in metal-oxide-semiconductor (MOS) capacitors depends on the metal electrode material. The metal/HfO2/Si and metal/HfO2/Ge capacitor were made using an atomic layer deposited HfO2 dielectric films and Mo, Ru, and Pt electrodes above Si substrate and Ti, Ru, and Pt electrodes above Ge substrate. The measured saturation capacitance was varied with electrode and evaluated to capacitance equivalent thickness (CET). In Si-based MOS capacitor, the CET value of the capacitor with Pt electrode is larger than those with Mo and Ru electrode. In addition, the CET is 27.4 A, 38.2 A, and 30.8 A for Ti, Ru, and Pt electrode, respectively, for Ge-based MOS capacitors. The CET variation with electrode is attributed the variation of dielectric constant of HfO2 dielectric and the difference of interfacial layer. The CET variation is well in agreement with the interfacial layer thickness taken by a transmission electron microscopy. The thickness variation of interfacial layer results from the oxygen gettering ability of the electrode even though they are apart.

  6. A third subunit in ancestral cytochrome c-dependent nitric oxide reductases.

    PubMed

    Bricio, C; Alvarez, L; San Martin, M; Schurig-Briccio, L A; Gennis, R B; Berenguer, J

    2014-08-01

    Reduction of NO to N2O by denitrifiying bacteria is catalyzed either by a monomeric quinol-nitric oxide reductase (qNor) or by a heterodimeric cytochrome c-dependent nitric oxide reductase (cNor). In ancient thermophilic bacteria belonging to the Thermales and Aquificales phylogenetic groups, the cluster encoding the cNor includes a small third gene (norH), in addition to those encoding homologues to the subunits of a typical cNor (norC and norB). We show in Thermus thermophilus that the three genes are cotranscribed in a single mRNA from an inducible promoter. The isolation of individual nor mutants and the production in vivo of His-tagged NorH protein followed by immobilized-metal affinity chromatography (IMAC) allowed us to conclude that NorH constitutes a third subunit of the cNor from T. thermophilus, which is involved in denitrification in vivo, likely allowing more efficient electron transport to cNor. PMID:24907324

  7. 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

  8. Temperature dependence of resistive switching behaviors in resistive random access memory based on graphene oxide film.

    PubMed

    Yi, Mingdong; Cao, Yong; Ling, Haifeng; Du, Zhuzhu; Wang, Laiyuan; Yang, Tao; Fan, Quli; Xie, Linghai; Huang, Wei

    2014-05-01

    We reported resistive switching behaviors in the resistive random access memory (RRAM) devices based on the different annealing temperatures of graphene oxide (GO) film as active layers. It was found that the resistive switching characteristics of an indium tin oxide (ITO)/GO/Ag structure have a strong dependence on the annealing temperature of GO film. When the annealing temperature of the GO film was 20 °C, the devices showed typical write-once-read-many-times (WORM) type memory behaviors, which have good memory performance with a higher ON/OFF current ratio (∼10(4)), the higher the high resistance state (HRS)/low resistance state (LRS) ratio (∼10(5)) and stable retention characteristics (>10(3) s) under lower programming voltage (-1 V and -0.5 V). With the increasing annealing temperature of GO film, the resistive switching behavior of RRAM devices gradually weakened and eventually disappeared. This phenomenon could be understood by the different energy level distributions of the charge traps in GO film, and the different charge injection ability from the Ag electrode to GO film, which is caused by the different annealing temperatures of the GO film. PMID:24739543

  9. Oxidative Stress and Cerebral Endothelial Cells: Regulation of the Blood-Brain-Barrier and Antioxidant Based Interventions

    PubMed Central

    Freeman, Linnea R; Keller, Jeffrey N

    2012-01-01

    While numerous lines of evidence point to increased levels of oxidative stress playing a causal role in a number of neurodegenerative conditions, our current understanding of the specific role of oxidative stress in the genesis and/or propagation of neurodegenerative diseases remains poorly defined. Even more challenging to the “oxidative stress theory of neurodegeneration” is the fact that many antioxidant-based clinical trials and therapeutic interventions have been largely disappointing in their therapeutic benefit. Together, these factors have led researchers to begin to focus on understanding the contribution of highly localized structures, and defined anatomical features, within the brain as the sites responsible for oxidative stress-induced neurodegeneration. This review focuses on the potential for oxidative stress within the cerebrovascular architecture serving as a modulator of neurodegeneration in a variety of pathological settings. In particular, this review highlights important implications for vascular-derived oxidative stress in the initiating and promoting pathophysiology in the brain, identifying new roles for cerebrovascular oxidative stress in a variety of brain disorders. PMID:22206999

  10. Different enzymes are involved in anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation in Thiobacillus denitrificans

    NASA Astrophysics Data System (ADS)

    Zhou, P.; Beller, H. R.

    2011-12-01

    Thiobacillus denitrificans is a widespread, obligate chemolithoautotrophic bacterium that is capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation. Both of these processes can mediate the mobility of uranium in contaminated aquifers and thereby influence the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. T. denitrificans has been found at uranium-contaminated sites, including a contaminated aquifer at Oak Ridge National Laboratory. We previously reported that two membrane-associated, diheme, c-type cytochromes (a c4 cytochrome, Tbd_0187, and a c5 cytochrome, Tbd_0146) were involved in nitrate-dependent U(IV) oxidation in T. denitrificans. To date, these are the only genes identified to be involved in this process. In this poster, we report on work with T. denitrificans focused on determining whether the enzymes that were demonstrated to be involved in anaerobic, nitrate-dependent U(IV) oxidation are also involved in nitrate-dependent Fe(II) oxidation. Using a genetic system in T. denitrificans that enables us to create insertion mutants and complement them in trans, we constructed a series of insertion mutants. These included strains with mutations in the genes known to be associated with U(IV) oxidation (Tbd_0146 and Tbd_0187) as well as other genes encoding membrane-associated c-type cytochromes (a group of proteins that we hypothesize to be catalyzing Fe(II) oxidation). Anaerobic cell suspension assays were carried out to determine whether any of these mutants were defective in nitrate-dependent Fe(II) oxidation. We observed that the Tbd_0146 and Tbd_0187 mutants were not defective in nitrate-dependent Fe(II) oxidation, nor were any of the other c-type cytochrome mutants tested (including a Tbd_0146-Tbd_0187 double mutant). The finding that different enzymes are associated with nitrate-dependent Fe(II) and U(IV) oxidation has led us to pursue genome-wide studies in T. denitrificans to determine the genes associated

  11. Nitric oxide triggers specific and dose-dependent cytosolic calcium transients in Arabidopsis

    PubMed Central

    Aboul-Enein, Ahmed M; Loake, Gary J

    2009-01-01

    Calcium (Ca2+) 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 ([Ca2+]cyt) was investigated. For this purpose, transgenic Arabidopsis seedlings constitutively expressing the luminescent Ca2+-sensitive protein apoaequorin (35S::APOAEQUORIN) was employed. In chemiluminescence and in vivo Ca2+ imaging assays, the NO-donor sodium nitroprusside (SNP) triggered a strong, instantaneous, reproducible, and dose-dependent rise in [Ca2+]cyt. Moreover, the observed rise in [Ca2+]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 [Ca2+]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 Ca2+ transient. This observation indicates that, in addition to the mobilization of [Ca2+]cyt, as an external source in response to NO treatment, there also exists an appreciable contribution of an as yet unidentified internal pool. PMID:19721746

  12. 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. PMID:26661480

  13. A Kinetic Study of Ozone and Nitric Oxides in Dielectric Barrier Discharges for O2/NOx Mixtures

    NASA Astrophysics Data System (ADS)

    Sun, Ji-zhong; T, Stirner; Wang, De-zhen

    2002-04-01

    A simple model is described to simulate kinetic processes in dielectric barrier discharges for O2/NOx mixtures. A threshold of ozone production found experimentally is confirmed by the calculations of this modeling, and the underlying chemical reaction mechanisms are discussed. It is also found that the effects of diffusion processes in the period of the lifetime of O atoms are not important to microdischarge channels with a large radius, i.e. larger than 150 μm.

  14. Nitric oxide dilates rat retinal blood vessels by cyclooxygenase-dependent mechanisms.

    PubMed

    Ogawa, Naoto; Mori, Asami; Hasebe, Masami; Hoshino, Maya; Saito, Maki; Sakamoto, Kenji; Nakahara, Tsutomu; Ishii, Kunio

    2009-10-01

    It has been suggested that nitric oxide (NO) stimulates the cyclooxygenase (COX)-dependent mechanisms in the ocular vasculature; however, the importance of the pathway in regulating retinal circulation in vivo remains to be elucidated. Therefore, we investigated the role of COX-dependent mechanisms in NO-induced vasodilation of retinal blood vessels in thiobutabarbital-anesthetized rats with and without neuronal blockade (tetrodotoxin treatment). Fundus images were captured with a digital camera that was equipped with a special objective lens. The retinal vascular response was assessed by measuring changes in diameter of the retinal blood vessel. The localization of COX and soluble guanylyl cyclase in rat retina was examined using immunohistochemistry. The NO donors (sodium nitroprusside and NOR3) increased the diameter of the retinal blood vessels but decreased systemic blood pressure in a dose-dependent manner. Treatment of rats with indomethacin, a nonselective COX inhibitor, or SC-560, a selective COX-1 inhibitor, markedly attenuated the vasodilation of retinal arterioles, but not the depressor response, to the NO donors. However, both the vascular responses to NO donors were unaffected by the selective COX-2 inhibitors NS-398 and nimesulide. Indomethacin did not change the retinal vascular and depressor responses to hydralazine, 8-(4-chlorophenylthio)-guanosine-3', 5'-cyclic monophosphate (a membrane-permeable cGMP analog) and 8-(4-chlorophenylthio)-adenosine-3', 5'-cyclic monophosphate (a membrane-permeable cAMP analog). Treatment with SQ 22536, an adenylyl cyclase inhibitor, but not ODQ, a soluble guanylyl cyclase inhibitor, significantly attenuated the NOR3-induced vasodilation of retinal arterioles. The COX-1 immunoreactivity was found in retinal blood vessels. The retinal blood vessel was faintly stained for soluble guanylyl cyclase, although the apparent immunoreactivities on mesenteric and choroidal blood vessels were observed. These results suggest

  15. 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. PMID:27180680

  16. 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...

  17. 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.

  18. Characterization of thermally oxidized Ta/GaAs Schottky barrier structures prepared by low energy RF sputtering with X-ray photoemission, TEM and optical transmittance measurements

    NASA Astrophysics Data System (ADS)

    Gladkov, P.; Varblianska, K.; Marinova, Ts.; Krastev, V.; Stoemenos, J.

    Schottky barrier Ta 2O 5/Ta/GaAs structures produced by RF magnetron sputtering of Ta onto "in situ" sputter etched GaAs substrates are the subject of the present investigation. The tantalum oxides formed directly during the process of thermal recovery of the structures contain predominantly Ta 2O 5 according to XPS data. The component distribution in these structures, formed under optimum recovery conditions with respect to the Schottky barrier parameters ( ΦB and η) has been studied by XPS and TEM. The applied conditions for thermal recovery and simultaneous oxidation are: isothermal annealing at temperatures 400-420°C for 100 min in an ambient of dry air and starting layers of 40 nm RF-sputtered Ta. The partial oxidation of the Ta layer during the heat treatment results in the formation of a thin layer of Ta 2O 5 on the top of the structure, followed by two layers: a mixture of Ta 2O 5 + Ta and a thin Schottky contact predominantly consisting of Ta. The total optical transmittance in the spectral range 0.7-1.1 μ of these three successive layers is ≥ 0.7. This result justifies the potential application of these structures in the creation of Schottky photodiodes in the visible and near-IR. It is established as well that at T ≥ 400°C GaAs and Ta start interacting resulting in the formation of intermetallic compounds of the type: Ta 5Ga, Ta 5Ga 3, and TaGa 3.

  19. 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

  20. 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.

  1. 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

  2. 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

  3. Graphene oxide-dependent growth and self-aggregation into a hydrogel complex of exoelectrogenic bacteria.

    PubMed

    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/cm(3) (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

  4. Self-Adaptive Spike-Time-Dependent Plasticity of Metal-Oxide Memristors.

    PubMed

    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

  5. Self-Adaptive Spike-Time-Dependent Plasticity of Metal-Oxide Memristors

    NASA Astrophysics Data System (ADS)

    Prezioso, M.; Merrikh Bayat, F.; Hoskins, B.; Likharev, K.; Strukov, D.

    2016-02-01

    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.

  6. Applicability of anaerobic nitrate-dependent Fe(II) oxidation to microbial enhanced oil recovery (MEOR).

    PubMed

    Zhu, Hongbo; Carlson, Han K; Coates, John D

    2013-08-01

    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. PMID:23799785

  7. Functional interaction of endothelial nitric oxide synthase with a voltage-dependent anion channel

    PubMed Central

    Sun, Jianxin; Liao, James K.

    2002-01-01

    Endothelium-derived nitric oxide (NO) is an important regulator of vascular function. NO is produced by endothelial NO synthase (eNOS) whose function is modulated, in part, by specific protein interactions. By coimmunoprecipitation experiments followed by MS analyses, we identified a human voltage-dependent anion/cation channel or porin as a binding partner of eNOS. The interaction between porin and eNOS was demonstrated by coimmunoprecipitation studies in nontransfected human endothelial cells and Cos-7 cells transiently transfected with eNOS and porin cDNAs. In vitro binding studies with glutathione S-transferase–porin indicated that porin binds directly to eNOS and that this interaction augmented eNOS activity. The calcium ionophore, A23187, and bradykinin, which are known to activate eNOS, markedly increased porin–eNOS interaction, suggesting a potential role of intracellular Ca2+ in mediating this interaction. Theses results indicate that the interaction between a voltage-dependent membrane channel and eNOS may be important for regulating eNOS activity. PMID:12228731

  8. The temperature dependence of H + OH recombination in phosphorus oxide containing post-combustion gases

    SciTech Connect

    Twarowski, A.

    1996-05-01

    The temperature dependence of the rate of H + OH recombination is experimentally investigated using laser photolysis of high-temperature (1,500--2,500 K) water vapor. Parametric adjustment of reaction rate constants to fit a simulated OH signal with the experimental OH decay data gives a three-body reaction rate constant for H + OH + M {yields} H{sub 2}O + M that is larger than expected at low temperature and lower at high temperatures. This result could have negative consequences for hypersonic propulsion systems since much of the thrust producing radical recombination occurs at high temperature. When POH{sub 3} combustion products are present in the photolyzed gas mixture at low concentration, the OH decay is much faster and dominated by catalytic reactions that include phosphorus oxides and acids. Parametric reaction rate analysis indicates that two reactions, H + PO{sub 2} {yields} HOPO and H + HOPO {yields} H{sub 2} + PO{sub 2} are responsible for the increase in the overall rate of H + OH recombination. The temperature dependence of the phosphine catalyzed recombination reaction is adequately described by the rate constant estimates previously reported.

  9. Dependence of the critical temperature in overdoped copper oxides on superfluid density

    DOE PAGESBeta

    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)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

  10. Plasma-Assisted Chemical Vapor Deposition of Titanium Oxide Films by Dielectric Barrier Discharge in TiCl4/O2/N2 Gas Mixtures

    NASA Astrophysics Data System (ADS)

    Niu, Jinhai; Zhang, Zhihui; Fan, Hongyu; Yang, Qi; Liu, Dongping; Qiu, Jieshan

    2014-07-01

    Low-pressure dielectric barrier discharge (DBD) TiCl4/O2 and N2 plasmas have been used to deposit titanium oxide films at different power supply driving frequencies. A homemade large area low pressure DBD reactor was applied, characterized by the simplicity of the experimental set-up and a low consumption of feed gas and electric power, as well as being easy to operate. Atomic force microscopy, scanning electron microscopy, energy dispersive spectroscopy, and contact angle measurements have been used to characterize the deposited films. Experimental results show all deposited films are uniform and hydrophilic with a contact angle of about 15°. Compared to titanium oxide films deposited in TiCl4/O2 gas mixtures, those in TiCl4/O2/N2 gas mixtures are much more stable. The contact angle of titanium oxide films in TiCl4/O2/N2 gas mixtures with the addition of 50% N2 and 20% TiCl4 is still smaller than 20°, while that of undoped titanium oxide films is larger than 64° when they are measured after one week. The low-pressure TiCl4/O2 plasmas consist of pulsed glow-like discharges with peak widths of several microseconds, which leads to the uniform deposition of titanium oxide films. Increasing a film thickness over several hundreds of nm leads to the film's fragmentation due to the over-high film stress. Optical emission spectra (OES) of TiCl4/O2 DBD plasmas at various power supply driving frequencies are presented.

  11. The FBXO4 Tumor Suppressor Functions as a Barrier to BrafV600E-Dependent Metastatic Melanoma

    PubMed Central

    Lee, Eric K.; Lian, Zhaorui; D'Andrea, Kurt; Letrero, Richard; Sheng, WeiQi; Liu, Shujing; Diehl, J. Nathaniel; Pytel, Dariusz; Barbash, Olena; Schuchter, Lynn; Amaravaradi, Ravi; Xu, Xiaowei; Herlyn, Meenhard; Nathanson, Katherine L.

    2013-01-01

    Cyclin D1–cyclin-dependent kinase 4/6 (CDK4/6) dysregulation is a major contributor to melanomagenesis. Clinical evidence has revealed that p16INK4A, an allosteric inhibitor of CDK4/6, is inactivated in over half of human melanomas, and numerous animal models have demonstrated that p16INK4A deletion promotes melanoma. FBXO4, a specificity factor for the E3 ligase that directs timely cyclin D1 proteolysis, has not been studied in melanoma. We demonstrate that Fbxo4 deficiency induces Braf-driven melanoma and that this phenotype depends on cyclin D1 accumulation in mice, underscoring the importance of this ubiquitin ligase in tumor suppression. Furthermore, we have identified a substrate-binding mutation, FBXO4 I377M, that selectively disrupts cyclin D1 degradation while preserving proteolysis of the other known FBXO4 substrate, TRF1. The I377M mutation and Fbxo4 deficiency result in nuclear accumulation of cyclin D1, a key transforming neoplastic event. Collectively, these data provide evidence that FBXO4 dysfunction, as a mechanism for cyclin D1 overexpression, is a contributor to human malignancy. PMID:24019069

  12. Treated effect of silymarin on vascular function of aged rats: Dependant on nitric oxide pathway.

    PubMed

    Demirci, Buket; Demir, Omer; Dost, Turhan; Birincioglu, Mustafa

    2013-11-01

    Abstract Context: Aging leads to endothelial dysfunction and vascular stiffness which are the main causes of many cardiovascular diseases. Previous reports have shown that the cell protective effect of silymarin (SM) is dependent on its antioxidant properties. Objectives: We investigated the effect of SM on vascular functions of aged rats and the involvement of nitric oxide or cyclooxygenase (COX) activity in this effect. Materials and methods: Isolated rat aortas were obtained from 22-month old rats. Each ring was incubated with SM (50 mg/L), SM/l-nitro-arginine methyl ester (100 μM, l-NAME) or SM/indomethacin (10 μM, INDO) in tissue bath. Three- to four-month-old rats were used as young controls. Endothelium-intact rings were precontracted with α-receptor agonist phenylephrine (0.001-30 µM) or voltage-dependent high potassium (40 mM), endothelium dependent/independent relaxant responses were obtained using acetylcholine (0.001-30 µM) and sodium nitroprusside (0.0001-3 µM), respectively. Results: Aging increased phenylephrine sensitivity (6.45 ± 0.08; 6.88 ± 0.09) and decreased KCl contraction (882 ± 118.4; 499 ± 80.4). SM treatment decreased the Emax of both agents (548 ± 109; 223 ± 48.9). Aging deteriorated acetylcholine relaxation (93.9 ± 2.09; 72.0 ± 2.56) and SM improved the response (86.3 ± 1.90). l-NAME prevented the SM effect whereas INDO was ineffective. Discussion and Conclusion: Immediate SM treatment partially restored endothelial dysfunction and vascular tone in aging. The possible mechanism might not be mediated by prostacyclin or the COX pathway in acute administration; the nitric oxide pathway and calcium antagonistic features of SM relate to its action on the vessel. PMID:24188646

  13. Relaxation Mechanism of Electrochromism of Tungsten-Oxide Film for Ultra-Multilayer Optical Recording Depending on Sputtering Conditions

    NASA Astrophysics Data System (ADS)

    Sato, Ryuji; Kawamura, Norikazu; Tokumaru, Haruki

    2007-06-01

    A tungsten-oxide single-layer film can be colored densely by using dilute sulfuric acid as a liquid electrolyte instead of the multilayer electrochromic cell. The transmissivity contrast before and after coloration reaches 70% at a wavelength of 405 nm. The bleaching relaxation time of a colored tungsten-oxide single-layer film is in the order of 1000 hours and depends on the sputtering power.

  14. 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.

  15. The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy.

    PubMed

    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

  16. 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.

  17. 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

  18. 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. PMID:25534813

  19. DFT investigations on AuVO3+, a barrier-free catalyst for oxidation of CO with O2

    NASA Astrophysics Data System (ADS)

    Zhang, Hao-Xu; Ding, Xun-Lei

    2016-08-01

    As an outstanding catalyst for CO oxidation at low temperatures, highly dispersed gold on metal oxides supports has long been the hot topic. And recently single-atom catalysts have attracted great interest. Thus here catalytic oxidation of CO with AuVO3+ was investigated with density functional theory calculations. The whole catalytic cycles can proceed naturally via the following processes: (i) AuVO3+ is subsequently reduced to AuVO2+ and AuVO+ under successive attacks from CO molecules trapped at the Au-site; (ii) AuVO+ can be oxidized by O2 trapped at the V-site, and the intermediate can be fully activated to regenerate AuVO3+; (iii) while for AuVO2+, successive attacks from a O2 molecule trapped at the V-site and a CO molecule trapped at the Au-site are required to finally regenerate AuVO3+. The single Au atom acts as both the favorable CO trapper and the electron reservoir during CO oxidation and O2 activation processes.

  20. Homoepitaxial graphene tunnel barriers for spin transport

    NASA Astrophysics Data System (ADS)

    Friedman, Adam

    Tunnel barriers are key elements for both charge-and spin-based electronics, offering devices with reduced power consumption and new paradigms for information processing. Such devices require mating dissimilar materials, raising issues of heteroepitaxy, interface stability, and electronic states that severely complicate fabrication and compromise performance. Graphene is the perfect tunnel barrier. It is an insulator out-of-plane, possesses a defect-free, linear habit, and is impervious to interdiffusion. Nonetheless, true tunneling between two stacked graphene layers is not possible in environmental conditions (magnetic field, temperature, etc.) usable for electronics applications. However, two stacked graphene layers can be decoupled using chemical functionalization. We demonstrate successful tunneling, charge, and spin transport with a fluorinated graphene tunnel barrier on a graphene channel. We show that while spin transport stops short of room temperature, spin polarization efficiency values are the highest of any graphene spin devices. We also demonstrate that hydrogenation of graphene can also be used to create a tunnel barrier. We begin with a four-layer stack of graphene and hydrogenate the top few layers to decouple them from the graphene transport channel beneath. We demonstrate successful tunneling by measuring non-linear IV curves and a weakly temperature dependent zero-bias resistance. We demonstrate lateral transport of spin currents in non-local spin-valve structures and determine spin lifetimes with the non-local Hanle effect to be commensurate with previous studies. The measured spin polarization efficiencies for hydrogenated graphene are higher than most oxide tunnel barriers on graphene, but not as high as with fluorinated graphene tunnel barriers. However, here we show that spin transport persists up to room temperature. Our results for the hydrogenated graphene tunnel barriers are compared with fluorinated tunnel barriers and we discuss the

  1. Highly Oxidizing Excited States of One-Electron Oxidized Guanine in DNA: Wavelength and pH Dependence

    PubMed Central

    Khanduri, Deepti; Adhikary, Amitava; Sevilla, Michael D.

    2011-01-01

    Excited states of one-electron oxidized guanine in DNA are known to induce hole transfer to the sugar moiety and on deprotonation result in neutral sugar radicals that are precursors of DNA-strand breaks. This work carried out in homogeneous aqueous glass (7.5 M LiCl) at low temperatures (77 to 175 K) shows the extent of photoconversion of one-electron oxidized guanine and the associated yields of individual sugar radicals and are crucially controlled by photon energy, protonation state, and strandedness of the oligomer. In addition to forming sugar radicals, highly oxidizing excited states of one-electron oxidized guanine are produced with 405 nm light at pH 5 and below that are able to oxidize chloride ion in the surrounding solution to form Cl2•− via an excited state hole transfer process. Among the various DNA model systems studied in this work, the maximum amount of Cl2•− is produced with ds (double stranded) DNA where the one-electron oxidized guanine exists in its cation radical (G•+:C) form. Thus, via excited state hole transfer, the dsDNA is apparently able to protect itself from cation radical excited states by transfer of damage to the surrounding environment. PMID:21381665

  2. 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. PMID:21801496

  3. Dependence of Heterogeneous OH Kinetics with Biomass Burning Aerosol Proxies on Oxidant Concentration and Relative Humidity

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Knopf, D. A.

    2013-12-01

    Chemical transformations of aerosol particles by heterogeneous reactions with trace gases such as OH radicals can influence particle physicochemical properties and lifetime, affect cloud formation, light scattering, and human health. Furthermore, OH oxidation can result in degradation of particle mass by volatilization reactions, altering the budget of volatile organic compounds (VOCs). However, the reactive uptake coefficient (γ) and particle oxidation degree can vary depending on several factors including oxidant concentration and relative humidity (RH). While RH can influence the extent of dissociation/ionization, it can also affect particle phase and thus oxidant diffusivity. Only one study so far has investigated the effect of RH on the rate of OH uptake to organic surfaces; however, the underlying processes affecting OH reactivity with organic aerosol under humidified conditions still remains elusive. Here, we determine the effect of RH on OH reactivity with laboratory-generated biomass burning aerosol (BBA) surrogate particles: levoglucosan and 4-methyl-5-nitrocatechol. The effect of OH concentration on γ for three common BBA molecular markers (levoglucosan, abietic acid, and nitroguaiacol) under dry conditions was investigated from [OH]≈107-1011 molecule cm-3, covering both [OH] in biomass burning plumes and [OH] commonly used in particle aging studies. Furthermore, key VOC reaction products and their production pathways resulting from BBA volatilization by OH were identified. OH radicals are produced using a microwave induced plasma (MIP) of H2 in He or Ar followed by reaction with O2, or by photolysis of O3 in the presence of H2O. A cylindrical rotating wall flow-tube reactor and fast-flow aerosol flow reactor are used for conducting kinetic studies. OH is detected using a Chemical Ionization Mass Spectrometer (CIMS) and a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) is employed for VOC analysis. γ decreases from 0.2-0.5 at

  4. 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.

  5. 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.

  6. Schottky barrier diodes of corundum-structured gallium oxide showing on-resistance of 0.1 mΩ·cm2 grown by MIST EPITAXY®

    NASA Astrophysics Data System (ADS)

    Oda, Masaya; Tokuda, Rie; Kambara, Hitoshi; Tanikawa, Tomochika; Sasaki, Takahiro; Hitora, Toshimi

    2016-02-01

    Thin-film corundum-structured gallium oxide (α-Ga2O3) Schottky barrier diodes (SBDs) were fabricated by growing α-Ga2O3 layers on sapphire substrates by the safe, low-cost, and energy-saving MIST EPITAXY® technique, followed by lifting off the α-Ga2O3 layers from the substrates. The SBDs exhibited on-resistance and breakdown voltage of 0.1 mΩ·cm2 and 531 V (SBD1) or 0.4 mΩ·cm2 and 855 V (SBD2), respectively. These results will encourage the future evolution of low-cost and high-performance SBDs with α-Ga2O3.

  7. Effects of sintering and mixed oxide growth on the interface cracking of air-plasma-sprayed thermal barrier coating system at high temperature

    NASA Astrophysics Data System (ADS)

    Lv, Bowen; Xie, Hua; Xu, Rong; Fan, Xueling; Zhang, Weixu; Wang, T. J.

    2016-01-01

    Sintering and mixed oxide (MO) growth significantly affect the thermal and mechanical properties of thermal barrier coating system (TBCs) in gas turbine at high temperature. In this work, we numerically analyzed the effects of sintering and MO growth on the interface cracking of TBCs. A thermal-elasto-viscoplastic constitutive model was introduced, in which the effect of sintering was studied using a spherical shell model. Based on the same spherical shell model and our previous experimental observations, we theoretically derived the evolution of relative density and applied this constitutive model to the sintering of ceramic coating. The numerical results showed that viscosity, initial porosity of ceramic and the growth rate of MO had significant effects on interface cracking. In contrast, the influence of initial pore size of ceramic coating was neglectable. Suggestions were also made for the choice of material during TBCs design.

  8. 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.

  9. Room-temperature detection of spin accumulation in silicon across Schottky tunnel barriers using a metal-oxide-semiconductor field effect transistor structure (invited)

    NASA Astrophysics Data System (ADS)

    Hamaya, K.; Ando, Y.; Masaki, K.; Maeda, Y.; Fujita, Y.; Yamada, S.; Sawano, K.; Miyao, M.

    2013-05-01

    Using a metal-oxide-semiconductor field effect transistor structure with a high-quality CoFe/n+-Si contact, we systematically study spin injection and spin accumulation in a nondegenerated Si channel with a doping density of ˜4.5 × 1015 cm-3 at room temperature. By applying the gate voltage (VG) to the channel, we obtain sufficient bias currents (IBias) for creating spin accumulation in the channel and observe clear spin-accumulation signals even at room temperature. Whereas the magnitude of the spin signals is enhanced by increasing IBias, it is reduced by increasing VG interestingly. These features can be understood within the framework of the conventional spin diffusion model. As a result, a room-temperature spin injection technique for the nondegenerated Si channel without using insulating tunnel barriers is established, which indicates a technological progress for Si-based spintronic applications with gate electrodes.

  10. 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. PMID:26406566

  11. 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.

  12. C-Type Natriuretic Peptide Induces Anti-contractile Effect Dependent on Nitric Oxide, Oxidative Stress, and NPR-B Activation in Sepsis

    PubMed Central

    Pernomian, Laena; Prado, Alejandro F.; Silva, Bruno R.; Azevedo, Aline; Pinheiro, Lucas C.; Tanus-Santos, José E.; Bendhack, Lusiane M.

    2016-01-01

    Aims: To evaluate the role of nitric oxide, reactive oxygen species (ROS), and natriuretic peptide receptor-B activation in C-type natriuretic peptide-anti-contractile effect on Phenylephrine-induced contraction in aorta isolated from septic rats. Methods and Results: Cecal ligation and puncture (CLP) surgery was used to induce sepsis in male rats. Vascular reactivity was conducted in rat aorta and resistance mesenteric artery (RMA). Measurement of survival rate, mean arterial pressure (MAP), plasma nitric oxide, specific protein expression, and localization were evaluated. Septic rats had a survival rate about 37% at 4 h after the surgery, and these rats presented hypotension compared to control-operated (Sham) rats. Phenylephrine-induced contraction was decreased in sepsis. C-type natriuretic peptide (CNP) induced anti-contractile effect in aortas. Plasma nitric oxide was increased in sepsis. Nitric oxide-synthase but not natriuretic peptide receptor-B expression was increased in septic rat aortas. C-type natriuretic peptide-anti-contractile effect was dependent on nitric oxide-synthase, ROS, and natriuretic peptide receptor-B activation. Natriuretic peptide receptor-C, protein kinase-Cα mRNA, and basal nicotinamide adenine dinucleotide phosphate (NADPH)-dependent ROS production were lower in septic rats. Phenylephrine and CNP enhanced ROS production. However, stimulated ROS production was low in sepsis. Conclusion: CNP induced anti-contractile effect on Phenylephrine contraction in aortas from Sham and septic rats that was dependent on nitric oxide-synthase, ROS, and natriuretic peptide receptor-B activation. PMID:27445832

  13. Nitric Oxide Exerts Basal and Insulin-Dependent Anorexigenic Actions in POMC Hypothalamic Neurons.

    PubMed

    Wellhauser, Leigh; Chalmers, Jennifer A; Belsham, Denise D

    2016-04-01

    The arcuate nucleus of the hypothalamus represents a key center for the control of appetite and feeding through the regulation of 2 key neuronal populations, notably agouti-related peptide/neuropeptide Y and proopimelanocortin (POMC)/cocaine- and amphetamine-regulated transcript neurons. Altered regulation of these neuronal networks, in particular the dysfunction of POMC neurons upon high-fat consumption, is a major pathogenic mechanism involved in the development of obesity and type 2 diabetes mellitus. Efforts are underway to preserve the integrity or enhance the functionality of POMC neurons in order to prevent or treat these metabolic diseases. Here, we report for the first time that the nitric oxide (NO(-)) donor, sodium nitroprusside (SNP) mediates anorexigenic actions in both hypothalamic tissue and hypothalamic-derived cell models by mediating the up-regulation of POMC levels. SNP increased POMC mRNA in a dose-dependent manner and enhanced α-melanocortin-secreting hormone production and secretion in mHypoA-POMC/GFP-2 cells. SNP also enhanced insulin-driven POMC expression likely by inhibiting the deacetylase activity of sirtuin 1. Furthermore, SNP enhanced insulin-dependent POMC expression, likely by reducing the transcriptional repression of Foxo1 on the POMC gene. Prolonged SNP exposure prevented the development of insulin resistance. Taken together, the NO(-) donor SNP enhances the anorexigenic potential of POMC neurons by promoting its transcriptional expression independent and in cooperation with insulin. Thus, increasing cellular NO(-) levels represents a hormone-independent method of promoting anorexigenic output from the existing POMC neuronal populations and may be advantageous in the fight against these prevalent disorders. PMID:26930171

  14. Exercise training improves functional sympatholysis in spontaneously hypertensive rats through a nitric oxide-dependent mechanism.

    PubMed

    Mizuno, Masaki; Iwamoto, Gary A; Vongpatanasin, Wanpen; Mitchell, Jere H; Smith, Scott A

    2014-07-15

    Functional sympatholysis is impaired in hypertensive animals and patients. Exercise training (ET) improves functional sympatholysis through a nitric oxide (NO)-dependent mechanism in normotensive rats. However, whether ET has similar physiological benefits in hypertension remains to be elucidated. Thus we tested the hypothesis that the impairment in functional sympatholysis in hypertension is reversed by ET through a NO-dependent mechanism. In untrained normotensive Wistar-Kyoto rats (WKYUT; n = 13), untrained spontaneously hypertensive rats (SHRUT; n = 13), and exercise-trained SHR (SHRET; n = 6), changes in femoral vascular conductance (FVC) were examined during lumbar sympathetic nerve stimulation (1, 2.5, and 5 Hz) at rest and during muscle contraction. The magnitude of functional sympatholysis (Δ%FVC = Δ%FVC muscle contraction - Δ%FVC rest) in SHRUT was significantly lower than WKYUT (1 Hz: -2 ± 4 vs. 13 ± 3%; 2.5 Hz: 9 ± 3 vs. 21 ± 3%; and 5 Hz: 12 ± 3 vs. 26 ± 3%, respectively; P < 0.05). Three months of voluntary wheel running significantly increased maximal oxygen uptake in SHRET compared with nontrained SHRUT (78 ± 6 vs. 62 ± 4 ml·kg(-1)·min(-1), respectively; P < 0.05) and restored the magnitude of functional sympatholysis in SHRET (1 Hz: 9 ± 2%; 2.5 Hz: 20 ± 4%; and 5 Hz: 34 ± 5%). Blockade of NO synthase (NOS) by N(G)-nitro-l-arginine methyl ester attenuated functional sympatholysis in WKYUT but not SHRUT. Furthermore, NOS inhibition significantly diminished the improvements in functional sympatholysis in SHRET. These data demonstrate that impairments in functional sympatholysis are normalized via a NO mechanism by voluntary wheel running in hypertensive rats. PMID:24816260

  15. 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

  16. 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.

  17. Dipyridamole enhances ischaemia-induced arteriogenesis through an endocrine nitrite/nitric oxide-dependent pathway

    PubMed Central

    Venkatesh, Prasanna K.; Pattillo, Christopher B.; Branch, Billy; Hood, Jay; Thoma, Steven; Illum, Sandra; Pardue, Sibile; Teng, Xinjun; Patel, Rakesh P.; Kevil, Christopher G.

    2010-01-01

    Aims Anti-platelet agents, such as dipyridamole, have several clinical benefits for peripheral artery disease with the speculation of angiogenic potential that could preserve ischaemic tissue viability, yet the effect of dipyridamole on ischaemic arteriogenesis or angiogenesis is unknown. Here we test the hypothesis that dipyridamole therapy augments arteriolar vessel development and function during chronic ischaemia. Methods and results Mice were treated with 200 mg/kg dipyridamole twice daily to achieve therapeutic plasma levels (0.8–1.2 µg/mL). Chronic hindlimb ischaemia was induced by permanent femoral artery ligation followed by measurement of tissue perfusion using laser Doppler blood flow along with quantification of vascular density, cell proliferation, and activation of nitric oxide (NO) metabolism. Dipyridamole treatment quickly restored ischaemic hindlimb blood flow, increased vascular density and cell proliferation, and enhanced collateral artery perfusion compared with control treatments. The beneficial effects of dipyridamole on blood flow and vascular density were dependent on NO production as dipyridamole did not augment ischaemic tissue reperfusion, vascular density, or endothelial cell proliferation in endothelial NO synthase (eNOS)-deficient mice. Blood and tissue nitrite levels were significantly higher in dipyridamole-treated mice compared with controls and eNOS−/− mice, verifying increased NO production that was regulated in a PKA-dependent manner. Conclusion Dipyridamole augments nitrite/NO production, leading to enhanced arteriogenesis activity and blood perfusion in ischaemic limbs. Together, these data suggest that dipyridamole can augment ischaemic vessel function and restore blood flow, which may be beneficial in peripheral artery disease. PMID:20061326

  18. Mitochondrial Sirt3 supports cell proliferation by regulating glutamine-dependent oxidation in renal cell carcinoma.

    PubMed

    Choi, Jieun; Koh, Eunjin; Lee, Yu Shin; Lee, Hyun-Woo; Kang, Hyeok Gu; Yoon, Young Eun; Han, Woong Kyu; Choi, Kyung Hwa; Kim, Kyung-Sup

    2016-06-01

    Clear cell renal carcinoma (RCC), the most common malignancy arising in the adult kidney, exhibits increased aerobic glycolysis and low mitochondrial respiration due to von Hippel-Lindau gene defects and constitutive hypoxia-inducible factor-α expression. Sirt3 is a major mitochondrial deacetylase that mediates various types of energy metabolism. However, the role of Sirt3 as a tumor suppressor or oncogene in cancer depends on cell types. We show increased Sirt3 expression in the mitochondrial fraction of human RCC tissues. Sirt3 depletion by lentiviral short-hairpin RNA, as well as the stable expression of the inactive mutant of Sirt3, inhibited cell proliferation and tumor growth in xenograft nude mice, respectively. Furthermore, mitochondrial pyruvate, which was used for oxidation in RCC, might be derived from glutamine, but not from glucose and cytosolic pyruvate, due to depletion of mitochondrial pyruvate carrier and the relatively high expression of malic enzyme 2. Depletion of Sirt3 suppressed glutamate dehydrogenase activity, leading to impaired mitochondrial oxygen consumption. Our findings suggest that Sirt3 plays a tumor-progressive role in human RCC by regulating glutamine-derived mitochondrial respiration, particularly in cells where mitochondrial usage of cytosolic pyruvate is severely compromised. PMID:27114304

  19. 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

  20. 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

  1. Support Morphology-Dependent Catalytic Activity of Pd/CeO₂ for Formaldehyde Oxidation.

    PubMed

    Tan, Hongyi; Wang, Jin; Yu, Shuzhen; Zhou, Kebin

    2015-07-21

    To eliminate indoor formaldehyde (HCHO) pollution, Pd/CeO2 catalysts with different morphologies of ceria support were employed. The palladium nanoparticles loaded on {100}-faceted CeO2 nanocubes exhibited much higher activity than those loaded on {111}-faceted ceria nanooctahedrons and nanorods (enclosed by {100} and {111} facets). The HCHO could be fully converted into CO2 over the Pd/CeO2 nanocubes at a GHSV of 10,000 h(-1) and a HCHO inlet concentration of 600 ppm at ambient temperature. The prepared catalysts were characterized by a series of techniques. The HRTEM, ICP-MS and XRD results confirmed the exposed facets of the ceria and the sizes (1-2 nm) of the palladium nanoparticles with loading amounts close to 1%. According to the Pd 3d XPS and H2-TPR results, the status of the Pd-species was dependent on the morphologies of the supports. The {100} facets of ceria could maintain the metallic Pd species rather than the {111} facets, which promoted HCHO catalytic combustion. The Raman and O 1s XPS results revealed that the nanorods with more defect sites and oxygen vacancies were responsible for the easy oxidation of the Pd-species and low catalytic activity. PMID:26120873

  2. Size-Dependent Electrocatalytic Activity of Free Gold Nanoparticles for the Glucose Oxidation Reaction.

    PubMed

    Hebié, Seydou; Napporn, Teko W; Morais, Cláudia; Kokoh, K Boniface

    2016-05-18

    Understanding the fundamental relationship between the size and the structure of electrode materials is essential to design catalysts and enhance their activity. Therefore, spherical gold nanoparticles (GNSs) with a mean diameter from 4 to 15 nm were synthesized. UV/Vis spectroscopy, transmission electron microscopy, and under-potential deposition of lead (UPDPb ) were used to determine the morphology, size, and surface crystallographic structure of the GNSs. The UPDPb revealed that their crystallographic facets are affected by their size and the growth process. The catalytic properties of these GNSs toward glucose electrooxidation were studied by cyclic voltammetry, taking into account the scan rate and temperature effects. The results clearly show the size-dependent electrocatalytic activity for glucose oxidation reactions that are controlled by diffusion. Small GNSs with an average size of 4.2 nm exhibited high catalytic activity. This drastic increase in activity results from the high specific area and reactivity of the surface electrons induced by their small size. The reaction mechanism was investigated by in situ Fourier transform infrared reflectance spectroscopy. Gluconolactone and gluconate were identified as the intermediate and the final reaction product, respectively, of the glucose electrooxidation. PMID:26879605

  3. Ascorbic acid and colon cancer: an oxidative stimulus to cell death depending on cell profile.

    PubMed

    Pires, Ana Salomé; Marques, Cláudia Raquel; Encarnação, João Carlos; Abrantes, Ana Margarida; Mamede, Ana Catarina; Laranjo, Mafalda; Gonçalves, Ana Cristina; Sarmento-Ribeiro, Ana Bela; Botelho, Maria Filomena

    2016-01-01

    Colorectal cancer is a major health problem worldwide with urgent need for new and effective anti-cancer approaches that allow treating, increasing survival and improving life quality of patients. At pharmacological concentrations, ascorbic acid (AA) exerts a selective cytotoxic effect, whose mechanism of cytotoxicity remains unsolved. It has been suggested that it depends on the production of extracellular hydrogen peroxide, using ascorbate radical as an intermediate. The aim of this study was to evaluate the effects induced by AA in three colon cancer cell lines, as well as, possible cell death mechanisms involved. Our results showed that pharmacological concentrations of AA induce anti-proliferative, cytotoxic and genotoxic effects on three colon cancer cell lines under study. We also found that AA can induce cell death by an increment of oxidative stress, but also mediating a ROS-independent mechanism, as observed in LS1034 cells. This work explores AA anti-tumoral effects and highlights its applicability in the treatment of CC, underlying the importance of proceeding to clinical trials. PMID:27083410

  4. Measurements of Location-Dependent Nitric Oxide Levels on Skin Surface in relation to Acupuncture Point

    PubMed Central

    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. PMID:23049611

  5. 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.

  6. Substrate-dependent nitric oxide synthesis by secreted endoplasmic reticulum aminopeptidase 1 in macrophages.

    PubMed

    Goto, Yoshikuni; Ogawa, Kenji; Nakamura, Takahiro J; Hattori, Akira; Tsujimoto, Masafumi

    2015-06-01

    In this study, we examined the role of aminopeptidases with reference to endoplasmic reticulum aminopeptidase 1 (ERAP1) in nitric oxide (NO) synthesis employing murine macrophage cell line RAW264.7 cells activated by lipopolysaccharide (LPS) and interferon (IFN)-γ and LPS-activated peritoneal macrophages derived from ERAP1 knockout mouse. When NO synthesis was measured in the presence of peptides having N-terminal Arg, comparative NO synthesis was seen with that measured in the presence of Arg. In the presence of an aminopeptidase inhibitor amastatin, NO synthesis in activated RAW264.7 cells was significantly decreased. These results suggest that aminopeptidases are involved in the NO synthesis in activated RAW264.7 cells. Subsequently, significant reduction of NO synthesis was observed in ERAP1 knockdown cells compared with wild-type cells. This reduction was rescued by exogenously added ERAP1. Furthermore, when peritoneal macrophages prepared from ERAP1 knockout mouse were employed, reduction of NO synthesis in knockout mouse macrophages was also attributable to ERAP1. In the presence of amastatin, further reduction was observed in knockout mouse-derived macrophages. Taken together, these results suggest that several aminopeptidases play important roles in the maximum synthesis of NO in activated macrophages in a substrate peptide-dependent manner and ERAP1 is one of the aminopeptidases involved in the NO synthesis. PMID:25577645

  7. Size dependent nonlinear optical properties of spin coated zinc oxide-polystyrene nanocomposite films

    NASA Astrophysics Data System (ADS)

    Jeeju, Pullarkat P.; Jayalekshmi, S.; Chandrasekharan, K.; Sudheesh, P.

    2012-11-01

    Using simple wet chemical method at room temperature, zinc oxide (ZnO) nanoparticles embedded in polystyrene (PS) matrix were synthesized. The size of the ZnO nanoparticles could be varied by varying the precursor concentration, reaction time and stirring speed. Transparent films of ZnO/PS nanocomposites of thickness around 1 μm were coated on ultrasonically cleaned glass substrates by spin coating. The optical absorptive nonlinearity in ZnO/PS nanocomposite films was investigated using open aperture Z-scan technique with nanosecond laser pulses at 532 nm. The results indicate optical limiting type nonlinearity in the films due to two-photon absorption in ZnO. These films also show a self-defocusing type negative nonlinear refraction in closed aperture Z-scan experiment. The observed nonlinear absorption is strongly dependent on particle size and the normalized transmittance could be reduced to as low as 0.43 by the suitable choice of the ZnO nanoparticle size. These composite films can hence be used as efficient optical limiters for sensor protection. The much-pronounced nonlinear response of these composite films, compared to pure ZnO, combined with the improved stability of ZnO nanoparticles in the PS matrix offer prospects of application of these composite films in the fabrication of stable non-linear optical devices.

  8. First-principles simulation on wire diameter dependence of piezoresistivity in zinc oxide nanowires

    NASA Astrophysics Data System (ADS)

    Nakamura, Koichi

    2015-06-01

    The wire dependence of piezoresistivity in wurtzite-type zinc oxide (ZnO) nanowires with a <0001> orientation has been simulated on the basis of the first-principles calculations of model structures. The strain responses to the carrier conductivity of n- or p-doped semiconducting wurtzite-ZnO<0001> nanowire models were calculated using band carrier densities and their corresponding effective masses derived from a one-dimensional band diagram by our original procedure. In this simulation, the conductivities of p-doped thin nanowire models change drastically owing to a longitudinal uniaxial strain because of either the redistribution of holes among subbands with completely different effective masses or the change in the effective mass. As a result, high positive longitudinal gauge factors and piezoresistance coefficients were obtained. On the other hand, for thick nanowire models with wire diameters of more than 1.5 nm, the piezoresistivity of the nanowire itself is essentially low in both the n- and p-doped states.

  9. 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. PMID:26796703

  10. Chromium oxide nanoparticle-induced genotoxicity and p53-dependent apoptosis in human lung alveolar cells.

    PubMed

    Senapati, Violet Aileen; Jain, Abhishek Kumar; Gupta, Govind Sharan; Pandey, Alok Kumar; Dhawan, Alok

    2015-10-01

    Chromium oxide (Cr2 O3 ) nanoparticles (NPs) are being increasingly used as a catalyst for aromatic compound manufacture, abrading agents and as pigments (e.g., Viridian). Owing to increased applications, it is important to study the biological effects of Cr2 O3 NPs on human health. The lung is one of the main exposure routes to nanomaterials; therefore, the present study was designed to determine the genotoxic and apoptotic effect of Cr2 O3 NPs in human lung epithelial cells (A549). The study also elucidated the molecular mechanism of its toxicity. Cr2 O3 NPs led to DNA damage, which was deduced by comet assay and cytokinesis block micronucleus assay. The damage could be mediated by the increased levels of reactive oxygen species. Further, the oxygen species led to a decrease in mitochondrial membrane potential and an increase in the ratio of BAX/Bcl-2 leading to mitochondria-mediated apoptosis induced by Cr2 O3 NPs, which ultimately leads to cell death. Hence, there is a need of regulations to be imposed in NP usage. The study provided insight into the caspase-dependent mechanistic pathway of apoptosis. PMID:26086747

  11. 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

    2016-04-01

    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. PMID:26943499

  12. Transport of Sulfide-Reduced Graphene Oxide in Saturated Quartz Sand: Cation-Dependent Retention Mechanisms.

    PubMed

    Xia, Tianjiao; Fortner, John D; Zhu, Dongqiang; Qi, Zhichong; Chen, Wei

    2015-10-01

    We describe how the reduction of graphene oxide (GO) via environmentally relevant pathways affects its transport behavior in porous media. A pair of sulfide-reduced GOs (RGOs), prepared by reducing 10 mg/L GO with 0.1 mM Na2S for 3 and 5 days, respectively, exhibited lower mobility than did parent GO in saturated quartz sand. Interestingly, decreased mobility cannot simply be attributed to the increased hydrophobicity and aggregation upon GO reduction because the retention mechanisms of RGOs were highly cation-dependent. In the presence of Na(+) (a representative monovalent cation), the main retention mechanism was deposition in the secondary energy minimum. However, in the presence of Ca(2+) (a model divalent cation), cation bridging between RGO and sand grains became the most predominant retention mechanism; this was because sulfide reduction markedly increased the amount of hydroxyl groups (a strong metal-complexing moiety) on GO. When Na(+) was the background cation, increasing pH (which increased the accumulation of large hydrated Na(+) ions on grain surface) and the presence of Suwannee River humic acid (SRHA) significantly enhanced the transport of RGO, mainly due to steric hindrance. However, pH and SRHA had little effect when Ca(2+) was the background cation because neither affected the extent of cation bridging that controlled particle retention. These findings highlight the significance of abiotic transformations on the fate and transport of GO in aqueous systems. PMID:26348539

  13. [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%. PMID:24946599

  14. 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.

  15. A seven-degree-of-freedom, time-dependent quantum dynamics study on the energy efficiency in surmounting the central energy barrier of the OH + CH{sub 3} → O + CH{sub 4} reaction

    SciTech Connect

    Yan, Pengxiu; Wang, Yuping; Li, Yida; Wang, Dunyou

    2015-04-28

    A time-dependent, quantum reaction dynamics calculation with seven degrees of freedom was carried out to study the energy efficiency in surmounting the approximate center energy barrier of OH + CH{sub 3}. The calculation shows the OH vibration excitations greatly enhance the reactivity, whereas the vibrational excitations of CH{sub 3} and the rotational excitations hinder the reactivity. On the basis of equal amount of total energy, although this reaction has a slight early barrier, it is the OH vibrational energy that is the dominate force in promoting the reactivity, not the translational energy. The studies on both the forward O + CH{sub 4} and reverse OH + CH{sub 3} reactions demonstrate, for these central barrier reactions, a small change of the barrier location can significantly change the energy efficacy roles on the reactivity. The calculated rate constants agree with the experimental data.

  16. Selective Silicidation of Co Using Silane or Disilane for Anti-Oxidation Barrier Layer in Cu Metallization

    NASA Astrophysics Data System (ADS)

    Noda, Suguru; Hirai, Rika; Komiyama, Hiroshi; Shimogaki, Yukihiro

    2004-09-01

    Aiming to realize a conductive passivation layer for copper interconnection, the solid-gas reactions of cobalt films with silane and with disilane to form cobalt silicides are experimentally investigated. X-ray photoelectron spectroscopy revealed that cobalt silicides layers of up to 6 nm thickness can be selectively formed in the reaction at 473-673 K within 5 min without detectable silicon deposition on silicon dioxide, a common inter-metal dielectric layer. Rapid thermal oxidation experiments revealed that the silicided cobalt layers had better anti-oxidation performance than untreated cobalt layers, and the effect of silicidation was to suppress copper out-diffusion through the cobalt layers. Because cobalt-based alloys can be selectively electroless-plated on copper, selective silicidation of cobalt layers will be easily incorporated into device processing.

  17. Oxidation of Met(144) and Met(145) in Calmodulin Blocks Calmodulin Dependent Activation of the Plasma Membrane Ca-ATPase.

    SciTech Connect

    Bartlett, Ryan K.; Urbauer, Ramona J.; Anbanandam, A; Smallwood, Heather S.; Urbauer, Jeffrey L.; Squier, Thomas C.

    2003-04-15

    Methionine oxidation in calmodulin (CaM) isolated from senescent brain results in an inability to fully activate the plasma membrane (PM) Ca-ATPase which may contribute to observed increases in cytosolic calcium levels under conditions of oxidative stress and biological aging. To identify the functional importance of the oxidation of Met-144 and Met-145 near the carboxyl-terminus of CaM, we have used site-directed mutagenesis to substitute leucines for methionines at other positions in CaM, permitting the site-specific oxidation of Met-144 and Met-145. Prior to the oxidation, the CaM-dependent activation of the PM-CA-ATPase by these CaM mutants is similar to that of wild-type CaM. Likewise, oxidation of individual methionines has a minimal effect on the CaM concentration necessary for half-maximal activation of the PM-Ca-ATPase. These results are consistent with previous suggestions that no single methionine within CaM is essential for activation of the PM-CA-ATPase. Oxidation of either Met-144 or Met-145 or all nine methionines in CaM results in an equivalent inhibition of the PM-Ca-ATPase, resulting in a 50-60% reduction in the level of enzyme activation. Oxidation of Met-144 is largely responsible for the decreased extent of enzyme activation, suggesting that this site is critical in modulating the sensitivity of CaM to oxidant-induced loss-of-function. These results are discussed in terms of a possible functional role for Met-144 and Met-145 in CaM as redox sensors that function to modulate calcium homeostasis and energy metabolism in response to conditions of oxidative stress.

  18. 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. PMID:22959434

  19. The oxidative cost of reproduction depends on early development oxidative stress and sex in a bird species.

    PubMed

    Romero-Haro, A A; Sorci, G; Alonso-Alvarez, C

    2016-06-29

    In the early 2000s, a new component of the cost of reproduction was proposed: oxidative stress. Since then the oxidative cost of reproduction hypothesis has, however, received mixed support. Different arguments have been provided to explain this. Among them, the lack of a life-history perspective on most experimental tests was suggested. We manipulated the levels of a key intracellular antioxidant (glutathione) in captive zebra finches (Taeniopygia guttata) during a short period of early life and subsequently tested the oxidative cost of reproduction. Birds were allowed to mate freely in an outdoor aviary for several months. We repeatedly enlarged or reduced their broods to increase or reduce, respectively, breeding effort. Birds whose glutathione levels were reduced during growth showed higher erythrocyte resistance to free radical-induced haemolysis when forced to rear enlarged broods. This supports the hypothesis predicting the occurrence of developing programmes matching early and adult environmental conditions to improve fitness. Moreover, adult males rearing enlarged broods endured higher plasma levels of lipid oxidative damage than control males, whereas adult females showed the opposite trend. As most previous studies reporting non-significant or opposite results used females only, we also discuss some sex-related particularities that may contribute to explain unexpected results. PMID:27358368

  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. POTENTIATING AND PROTECTIVE EFFECTS OF ASCORBATE ON OXIDATIVE STRESS DEPENDS UPON DIETARY IRON CONCENTRATION FED TO C3H MICE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ascorbic acid (AA) is an antioxidant that in the presence of iron and hydrogen peroxide increases the production of hydroxyl radicals in vitro. Whether AA has similar pro-oxidant properties in vivo may depend upon the relative balance of iron and ascorbic acid concentrations. In this study, C3H mice...

  2. 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. PMID:26928046

  3. Characterization of vanadate-dependent NADH oxidation activity and isolation of yeast DNA which complements a class 1 vanadate resistance mutation

    SciTech Connect

    Minasi, L.E.

    1989-01-01

    A vanadate-dependent NADH oxidation activity has been characterized in plasma membranes from the yeast S cerevisiae. NADH oxidation activity was maximally stimulated at pH 5.0 in phosphate buffer. NADH oxidation was not dependent on the concentration of plasma membranes. The vanadate-dependent NADH oxidation activity was abolished under anaerobic conditions and the concomitant uptake of oxygen occurred during NADH oxidation. The activity was inhibited by superoxide dismutase and stimulated by the presence of paraquat. These results indicate that the vanadate stimulation of NADH oxidation in yeast plasma membranes occurs as a result of the vanadate-dependent oxidation of NADH by superoxide, generated by a plasma membrane NADH oxidase. {sup 51}V-NMR results indicated that a phosphate-vanadate anhydride was the stimulatory species in pH 5.0 and pH 7.0 phosphate buffer. Yeast DNA has been isolated which complements a class 1 vanadate resistance mutation.

  4. 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

  5. Oxide thickness dependence of resistive switching characteristics for Ni/HfOx/Pt resistive random access memory device

    NASA Astrophysics Data System (ADS)

    Ito, Daisuke; Hamada, Yoshihumi; Otsuka, Shintaro; Shimizu, Tomohiro; Shingubara, Shoso

    2015-06-01

    The switching process of the conductive filament formed in Ni/HfOx/Pt resistive random access memory (ReRAM) devices were studied. We evaluated the oxide thickness dependence and temperature dependence of voltage for the Forming, Set and Reset operations for HfOx layers whose thickness are between 3.3 and 6.5 nm. The resistance of conductive filaments showed typical metallic behavior, which suggests Ni filament formation in the HfOx layer. There is a clear dependence of switching voltages for the Set and Reset processes on oxide thickness, which implies that the formation and rupture of conductive filaments occur in the entire thickness range of the HfOx layer. This finding differs from that of a previous study by Yang, which suggests the existence of a constant-thickness switching region. It is suggested that the thickness of the switching region in HfOx may be larger than 6.5 nm.

  6. Stability and migration barriers of small vanadium oxide clusters on the CeO2(111) surface studied by density functional theory.

    PubMed

    Paier, Joachim; Kropp, Thomas; Penschke, Christopher; Sauer, Joachim

    2013-01-01

    By virtue of periodic density functional theory, we investigate structure and thermodynamic stability of (VO)k and (VO2)k (k = 1, 2, 3) clusters deposited on the CeO2(111) surface, which serve as models for the very active sub-monolayer vanadia catalyst on a ceria support. We find V always completely oxidized (oxidation state +5) and coordinated to four O atoms. As a consequence, Ce4+ is (partially) reduced to Ce3+. Thus, localized Ce-4f states are populated, which requires an onsite U-term (PBE+U) to avoid over-delocalization off-electrons. Importantly, trimers of VO2 were found to be extraordinarily stable (agglomeration energy: -1.68 eV), whereas aggregation of VO species on CeO2(111) is thermodynamically clearly unfavourable (agglomeration energy: 3.45 eV). As a consequence a large area of the VnOm phase diagram (for relevant temperatures) is dominated by the VO2 trimer. The latter is less active towards reduction/oxidation than the active monomer and dimer of VO2, which are not present in the phase diagram at all, although directly observed by recent STM measurements. This suggests that kinetic effects hinder VO2 to grow into larger oligomers. The lowest migration energy barrier we found is as high as 1.95 eV, which indicates that adsorbed monomeric VO2 is "kinetically locked" at low temperatures and explains why monomers are stabilized on the ceria surface. PMID:24015586

  7. Parallel activation of mitochondrial oxidative metabolism with increased cardiac energy expenditure is not dependent on fatty acid oxidation in pigs

    PubMed Central

    Zhou, Lufang; Cabrera, Marco E; Huang, Hazel; Yuan, Celvie L; Monika, Duda K; Sharma, Naveen; Bian, Fang; Stanley, William C

    2007-01-01

    Steady state concentrations of ATP and ADP in vivo are similar at low and high cardiac workloads; however, the mechanisms that regulate the activation of substrate metabolism and oxidative phosphorylation that supports this stability are poorly understood. We tested the hypotheses that (1) there is parallel activation of mitochondrial and cytosolic dehydrogenases in the transition from low to high workload, which increases NADH/NAD+ ratio in both compartments, and (2) this response does not require an increase in fatty acid oxidation (FAO). Anaesthetized pigs were subjected to either sham treatment, or an abrupt increase in cardiac workload for 5 min with dobutamine infusion and aortic constriction. Myocardial oxygen consumption and FAO were increased 3- and 2-fold, respectively, but ATP and ADP concentrations did not change. NADH-generating pathways were rapidly activated in both the cytosol and mitochondria, as seen in a 40% depletion in glycogen stores, a 3.6-fold activation of pyruvate dehydrogenase, and a 50% increase in tissue NADH/NAD+. Simulations from a multicompartmental computational model of cardiac energy metabolism predicted that parallel activation of glycolysis and mitochondrial metabolism results in an increase in the NADH/NAD+ ratio in both cytosol and mitochondria. FAO was blocked by 75% in a third group of pigs, and a similar increase in and the NAHD/NAD+ ratio was observed. In conclusion, in the transition to a high cardiac workload