Interacting kinetics of neutral and ionic species in an atmospheric-pressure helium-oxygen plasma with humid air impurities

We unravel the complex chemistry in both the neutral and ionic systems of a radio-frequency-driven atmospheric-pressure plasma in a helium-oxygen mixture (He-0.5% O) with air impurity levels from 0 to 500 ppm of relative humidity from 0% to 100% using a zero-dimensional, time-dependent global model. Effects of humid air impurity on absolute densities and the dominant production and destruction pathways of biologically relevant reactive neutral species are clarified. A few hundred ppm of air impurity crucially changes the plasma from a simple oxygen-dependent plasma to a complex oxygen-nitrogen-hydrogen plasma. The density of reactive oxygen species decreases from 10 to 10 cm, which in turn results in a decrease in the overall chemical reactivity. Reactive nitrogen species (10 cm ), atomic hydrogen and hydroxyl radicals (10-10 cm) are generated in the plasma. With 500 ppm of humid air impurity, the densities of positively charged ions and negatively charged ions slightly increase and the electron density slightly decreases (to the order of 10 cm). The electronegativity increases up to 2.3 compared with 1.5 without air admixture. Atomic hydrogen, hydroxyl radicals and oxygen ions significantly contribute to the production and destruction of reactive oxygen and reactive nitrogen species. © 2013 IOP Publishing Ltd.

Chemical kinetics and reactive species in atmospheric pressure helium-oxygen plasmas with humid-air impurities

In most applications helium-based plasma jets operate in an open-air environment. The presence of humid air in the plasma jet will influence the plasma chemistry and can lead to the production of a broader range of reactive species. We explore the influence of humid air on the reactive species in radio frequency (rf)-driven atmospheric-pressure helium-oxygen mixture plasmas (He-O, helium with 5000 ppm admixture of oxygen) for wide air impurity levels of 0-500 ppm with relative humidities of from 0% to 100% using a zero-dimensional, time-dependent global model. Comparisons are made with experimental measurements in an rf-driven micro-scale atmospheric pressure plasma jet and with one-dimensional semi-kinetic simulations of the same plasma jet. These suggest that the plausible air impurity level is not more than hundreds of ppm in such systems. The evolution of species concentration is described for reactive oxygen species, metastable species, radical species and positively and negatively charged ions (and their clusters). Effects of the air impurity containing water humidity on electronegativity and overall plasma reactivity are clarified with particular emphasis on reactive oxygen species. © 2013 IOP Publishing Ltd.

Discharge kinetics of inductively coupled oxygen plasmas:Experiment and model

In this paper, neutral and charged particle dynamics in both the capacitive and inductive modes of an inductively coupled oxygen discharge are presented. Langmuir probes, laser-assisted photodetachment and two-photon laser-induced fluorescence are employed to measure plasma parameters in the 13.56MHz system for a range of plasma powers and gas pressures. It is found that the capacitive mode is more electronegative with lower molecular dissociation compared with the inductive mode. However, the negative ion density in each mode is comparable. A maximum is observed in the negative ion density and fraction with pressure for both modes. The experimental measurements are supplemented by a global model, which includes capacitive and inductive coupling effects. The model and experiments demonstrate that negative ion loss is dominated by ion-ion recombination and electron detachment at low pressures (

Nanoscale mapping of oxygen vacancy kinetics in nanocrystalline Samarium doped ceria thin films

The position-dependent oxygen vacancy dynamics induced by a biased scanning probe microscopy tip in Samarium doped ceria thin films grown on MgO (100) substrates is investigated. The granularity of the samples gives rise to spatially dependent local electrochemical activity, as explored by electrochemical strain microscopy. The kinetics of the oxygen vacancy relaxation process is investigated separately for grain boundaries and grains. Higher oxygen vacancy concentration variation and slower diffusion are observed in the grain boundary regions as compared to the grains.

Effect of methanol concentration on oxygen reduction reaction activity of Pt/C catalysts

The oxygen reduction reaction (ORR) activity of Pt/C catalysts was investigated in electrolytes of 0.5 mol/L H2SO4 containing varying concentrations of methanol in a half-cell. It was found that the ORR activity was improved notably in an electrolyte of 0.5 mol/L H2SO4 containing 0.1 mol/L CH3OH as compared with that in 0.5 mol/L H2SO4, 0.5 mol/L H2SO4 containing 0.5 mol/L CH3OH, or 0.5 mol/L H2SO4 containing 1.0 mol/L CH3OH electrolytes. The same tendency for improved ORR activity was also apparent after commercial Nafion (R) NRE-212 membrane was hot-pressed onto the catalyst layers. The linear sweep voltammetry results indicate that the ORR activities of the Pt/C catalyst were almost identical in the 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH solution before and after coated with the Nafion (R) membrane. Electrochemical impedance spectroscopy results demonstrated that the resistance of the Nafion (R) membrane is smaller in the electrolyte of 0.5 mol/L H2SO4 + 0.1 mol/L CH3OH than in other electrolytes with oxygen gas feed. This exceptional property of the Nafion (R) membrane is worth investigating and can be applied in fuel cell stacks to improve the system performance. (c) 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Oxygen solubility in ionic liquids based on 1-alkyl-3-methylimidazolium cations

This work presents the results of oxygen solubility in ionic liquids based on 1-alkyl-3-methylimidazolium cations. Solubility measurements have been carried out in gasometric apparatus at 22, 50 and 90 degrees C under atmospheric pressure. We report the Henry's constants. In general the occurrence of carbon-fluorine bonds and carbon-hydrogen bonds in ionic liquids (ILs) which can create hydrogen bonds with dissolved oxygen, significantly affects the growth of value of solubility constant K-H. Additionally, the stability of ILs towards molecular oxygen was tested. All ILs used in this study were stable in the presence of oxygen and free-radical initiator.

RuxNb1-xO2 catalyst for the oxygen evolution reaction in proton exchange membrane water electrolysers

Bimetallic catalyst system of ruthenium oxide (RuO) and niobium oxide (NbO) was prepared using the Adams method and the hydrolysis method. Physical and electrochemical characterizations of the catalysts were studied using X-ray diffraction (XRD), Scanning electron microscopy (SEM), cyclic voltammogram (CV) and polarization measurements. NbO addition to RuO was found to increase the stability of RuO. In Adams method the sodium nitrate was found to be forming complex with NbO at high temperature reaction. This makes Adams method unsuitable for the synthesis of RuO -NbO bimetallic system. Hydrolysis method on other hand does not have this problem. But a proper mixture of two oxides was not obtained in hydrolysis method. A lower crystallite size for bimetallic system was obtained with Adams method compared to hydrolysis method. RuO prepared by Adams method had higher activity compared to the hydrolysis counterpart in electrolyzer operation with nafion membrane. A cell voltage of 1.62 V was obtained with RuO (A) at 1 A/cm. A higher stability for RuNbO(A) compared to RuO(A) was observed in continuous cyclic voltammogram and electrolyzer cell test. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Investigation of supported IrO2 as electrocatalyst for the oxygen evolution reaction in proton exchange membrane water electrolyser

Indium tin oxide (ITO) was used as a support for IrO2 catalyst in the oxygen evolution reaction. IrO2 nanoparticles were deposited in various loading on commercially available ITO nanoparticle, 17–28 nm in size using the Adam's fusion method. The prepared catalysts were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area of the support (35 m2/g) was 3 times lower than the unsupported IrO2 (112.7 m2/g). The surface area and electronic conductivity of the catalysts were predominantly contributed by the IrO2. The supported catalysts were tested in a membrane electrode assembly (MEA) for electrolyser operation. The 90% IrO2-ITO gave similar performance (1.74 V@1 A/cm2) to that of the unsupported IrO2 (1.73 V@1 A/cm2) in the MEA polarisation test at 80 °C with Nafion 115 membrane which was attributed to a better dispersion of the active IrO2 on the electrochemically inactive ITO support, giving rise to smaller catalyst particle and thereby higher surface area. Large IrO2 particles on the support significantly reduced the electrode performance. A comparison of TiO2 and ITO as support material showed that, 60% IrO2 loading was able to cover the support surface and giving sufficient conductivity to the catalyst.

SN 2010LP - A type IA supernova from a violent merger of two carbon-oxygen white dwarfs

SN 2010lp is a subluminous Type Ia supernova (SN Ia) with slowly evolving lightcurves. Moreover, it is the only subluminous SN Ia observed so far that shows narrow emission lines of [O I] in late-time spectra, indicating unburned oxygen close to the center of the ejecta. Most explosion models for SNe Ia cannot explain the narrow [O I] emission. Here, we present hydrodynamic explosion and radiative transfer calculations showing that the violent merger of two carbon-oxygen white dwarfs of 0.9 and 0.76 M adequately reproduces the early-time observables of SN 2010lp. Moreover, our model predicts oxygen close to the center of the explosion ejecta, a pre-requisite for narrow [O I] emission in nebular spectra as observed in SN 2010lp. © 2013. The American Astronomical Society. All rights reserved.

Irradiation of oxygen and water ices at by 4 keV singly and doubly charged ions; sputtering and molecular synthesis

The icy surfaces of dust grains in the Interstellar Medium and those of comets, satellites and Kuiper Belt Objects are continuously exposed tophoton and charged particle irradiation. These energetic particles maysputter and induce chemical changes in the ices and the underlyingsurfaces.In the present work 258 nm thick O2 and H2O ices were deposited at 10 K with the thickness measured by a laser interferometer method. Asimple model fit to the reflected laser intensity as measured by aphotodiode detector enabled the refractive index of the ices to bedetermined. The ices were then irradiated with various singly and doublycharged ions such as He+, 13C+, N+, O+ , Ar+, 13C2+, N2+ and O2+ at 4keV. The decrease in ice thickness as a function of ion dose wasmonitored by a laser interferometer and the model used to determine thesputtering yield as shown in Figure 1.In the case of O2 ice thesputtering yields increased with increasing ion mass in good agreementwith a model calculation [Fama, J, Shi, R.A Baragiola, Surface Sci.,602, 156 (2007)]. In the case of O2 ice, O2+ has a significant lowersputtering yield when compared to O+. The sputtering yields for O2 icewere found to be at least 9 times larger compared to those for H2O ice.For H2O ice the sputter yields for C, N and O ions were found todecrease with increasing mass. Doubly charged C, N and O ions which werefound to have the same sputtering yield as the singly charged ionswithin the experimental errors. A preliminary TPD study was carried outusing a QMS to detect the desorbed species from water ice afterirradiation by 6 × 10^15 ions of 13C+ and 13C2+. The formation of13CO and 13CO2 was observed with the yield of 13CO almost of a factor of100 larger than of 13CO2. This is in contrast to our earlier work whereonly CO¬2 was observed.

Quantification of singlet oxygen generation from photodynamic hydrogels

Recently, we described a series of novel porphyrin-impregnated hydrogels capable of producing microbicidal singlet oxygen (1O2) on photoactivation. Indirect assessment of the efficacy of 1O2 production from such hydrogels has been previously described using microbiological techniques, but here we report a novel, direct method of quantification. Anthracene-9,10-dipropionic acid (ADPA) is known to irreversibly form an endoperoxide on reaction with 1O2, causing photobleaching of its absorbance band at approximately 378 nm. Here, the reaction of this probe is exploited in a novel way to provide a simple, inexpensive, and convenient measurement of 1O2 generation from the surface of porphyrin-incorporated photosensitising hydrogels, with the ability to account for effects due to hydrogel porosity. Ingress of the probe into the materials was observed, with rates of up to 3.83 x 103 s-1. This varied by up to 200-fold with material composition and surface modification. Rates of 1O2 generation in these porphyrin-incorporated hydrogels, after compensating for ADPA ingress, ranged from 1.86x103 – 5.86x103 s-1. This work demonstrates a simple and straightforward method for direct 1O2 quantification from porous materials, with general utility.

Assessing the environmental fate of selected polybrominated diphenyl ethers in the region surrounding the Zhuoshui River of Taiwan based on an Equilibrium Constant fugacity model

Polybrominated diphenyl ethers (PBDEs) are a group of flame retardants that have been in use since the 1970s. They are included in the list of hazardous substances known as persistent organic pollutants (POPs) because they are extremely hazardous to the environment and human health. PBDEs have been extensively used in industry and manufacturing in Taiwan, thus its citizens are at high risk of exposure to these chemicals.
An assessment of the environmental fate of these compounds in the Zhuoshui river and Changhua County regions of western Taiwan, and also including the adjacent area of the Taiwan Strait, was conducted for three high risk congeners, BDE-47, -99 and -209, to obtain information regarding the partitioning, advection, transfer and long range transport potential of the PBDEs in order to identify the level of risk posed by the pollutants in this region.
The results indicate that large amounts of PBDEs presently reside in all model compartments – air, soil, water, and sediment – with particularly high levels found in air and especially in sediment. The high levels found in sediment, particularly for BDE-209, are significant, since there is the threat of these pollutants entering the food chain, either directly through benthic feeding, or through resuspension and subsequent feeding in the pelagic region of the water column which is a distinct possibility in the strong currents found within the Taiwan Strait. Another important result is that a substantial portion of emissions leave the model domain directly through advection, particularly for BDE-47 (58%) and BDE-209 (75%), thus posing a risk to adjacent communities.
Model results were generally in reasonable agreement with available measured concentrations. In air, model concentrations are in reasonably good agreement with available measured values. For both BDE-47 and -99, model concentrations are a factor of 2-3 higher and BDE-209 within the range of measured values. In soil, model results are somewhat less than measured values. In sediment, model results are at the high end of measured values.

Small GTPase RhoA and its effector rho kinase mediate oxygen glucose deprivation-evoked in vitro cerebral barrier dysfunction

BACKGROUND AND PURPOSE: Enhanced vascular permeability attributable to disruption of blood-brain barrier results in the development of cerebral edema after stroke. Using an in vitro model of the brain barrier composed of human brain microvascular endothelial cells and human astrocytes, this study explored whether small GTPase RhoA and its effector protein Rho kinase were involved in permeability changes mediated by oxygen-glucose deprivation (OGD), key pathological phenomena during ischemic stroke.

METHODS: OGD increased RhoA and Rho kinase protein expressions in human brain microvascular endothelial cells and human astrocytes while increasing or unaffecting that of endothelial nitric oxide synthase in respective cells. Reperfusion attenuated the expression and activity of RhoA and Rho kinase in both cell types compared to their counterparts exposed to equal periods of OGD alone while selectively increasing human brain microvascular endothelial cells endothelial nitric oxide synthase protein levels. OGD compromised the barrier integrity as confirmed by decreases in transendothelial electric resistance and concomitant increases in flux of permeability markers sodium fluorescein and Evan's blue albumin across cocultures. Transfection of cells with constitutively active RhoA also increased flux and reduced transendothelial electric resistance, whereas inactivation of RhoA by anti-RhoA Ig electroporation exerted opposite effects. In vitro cerebral barrier dysfunction was accompanied by myosin light chain overphosphorylation and stress fiber formation. Reperfusion and treatments with a Rho kinase inhibitor Y-27632 significantly attenuated barrier breakdown without profoundly altering actin structure.

CONCLUSIONS: Increased RhoA/Rho kinase/myosin light chain pathway activity coupled with changes in actin cytoskeleton account for OGD-induced endothelial barrier breakdown.